Material and method for making an electroconductive pattern

ABSTRACT

A material for making an electroconductive pattern, the material comprising a support and a light-exposure differentiable element, characterized in that the light-exposure differentiable element comprises an outermost layer containing a polyanion and a polymer or copolymer of a substituted or unsubstituted thiophene, and optionally a second layer contiguous with the outermost layer; and wherein the outermost layer and/or the optional second layer contains a light-sensitive component capable upon exposure of changing the removability of the exposed parts of the outermost layer relative to the unexposed parts of the outermost layer; and a method of making an electroconductive pattern on a support using the material for making an electroconductive pattern.

[0001] The application claims the benefit of U.S. ProvisionalApplication No. 60/214,415 filed Jun. 28, 2000.

FIELD OF THE INVENTION

[0002] The present invention relates to a material and a method formaking an electroconductive pattern.

BACKGROUND OF THE INVENTION

[0003] For the fabrication of flexible LC displays, electrolumin-escentdevices and photovoltaic cells transparent ITO (indium-tin oxide)electrodes are used. These electrodes are made by vacuum sputtering ofITO onto a substrate. This method involves high temperatures, up to 250°C., and therefore glass substrates are generally used. The is range ofpotential applications is limited, because of the high fabricationcosts, the low flexibility (pliability) and stretchability as aconsequence of the brittleness of the ITO layer and the glass substrate.Therefore the interest is growing in all-organic devices, comprisingplastic resins as a substrate and organic electroconductive polymerlayers as electrodes. Such plastic electronics allow the realization oflow cost devices with new properties (Physics World, March 1999,p.25-39). Flexible plastic substrates can be provided with anelectroconductive polymer layer by continuous roller coating methods(compared to batch process such as sputtering) and the resulting organicelectrodes enable the fabrication of electronic devices characterised bya higher flexibility and a lower weight.

[0004] The production and the use of electroconductive polymers such aspolypyrrole, polyaniline, polyacetylene, polyparaphenylene,polythiophene, polyphenylenevinylene, polythienylenevinylene andpolyphenylenesulphide are known in the art.

[0005] EP-A 440 957 discloses dispersions of polythiophenes, constructedfrom structural units of formula (I):

[0006] in which R¹ and R² independently of one another representhydrogen or a C₁₋₄-alkyl group or together form an optionallysubstituted C₁₋₄-alkylene residue, in the presence of polyanions.Furthermore, EP-A-686 662 discloses mixtures of A) neutralpolythiophenes with the repeating structural unit of formula (I),

[0007] in which R¹ and R² independently of one another representhydrogen or a C1-C4 alkyl group or together represent an optionallysubstituted C1-C4 alkylene residue, preferably an optionally with alkylgroup substituted methylene, an optionally with C1-C12-alkyl or phenylgroup substituted 1,2-ethylene residue or a 1,2-cyclohexene residue, andB) a di- or polyhydroxy- and/or carboxy groups or amide or lactam groupcontaining organic compound; and conductive coatings therefrom which aretempered at elevated temperature, preferably between 100 and 250° C.,during preferably 1 to 90 seconds to increase their resistancepreferably to <300 ohm/square.

[0008] EP-A 614 123 discloses a water-soluble electrically conductivecomposition of matter comprising a polyacid and a polymer comprising atleast one conjugated region composed of repeating units which contain aconjugated basic atom. However, as water-soluble electrically conductivepolymer comprising at least one conjugated region composed of repeatingunits which contain a conjugated basic atom, only polyaniline andsubstituted polyanilines are exemplified.

[0009] EP-A 382 046 discloses an electrically conductive resistmaterial, essentially comprising at least one ionic radiation-sensitivepolymer and a soluble electrically conductive oligomer or a solubleelectrically conductive polymer. Polymers of substituted thiophenes areexemplified, but no specific ionic radiation-sensitive polymers.

[0010] EP-A 338 786 discloses a negative working, photosensitive,overlay color proofing film which comprises, in order: (i) a transparentsubstrate; (ii) a photosensitive layer on the substrate, whichphotosensitive layer comprises a light sensitive, negative working,polymeric diazonium compound which is the polycondensation product of3-methoxy-4-diazodiphenylamine sulfate and 4,4′-bis-methoxymethyldiphenyl ether precipitated as the chloride salt, which diazoniumcompound is present in sufficient amount to photosensitize the layer;and a water insoluble, water swellable binder resin in sufficient amountto bind the layer components in a uniform film; and at least onecolorant in sufficient amount to uniformly color the layer; wherein uponimagewise exposure of the photosensitive layer to sufficient actinicradiation the film is capable of being developed with water alone.

[0011] Coated layers of organic electroconductive polymers can bestructured into patterns using known microlithography techniques. InWO-A-97 18944 a process is described wherein a positive or negativephotoresist is applied on top of a coated layer of an organicelectroconductive polymer, and after the steps of selectively exposingthe photoresist to UV light, developing the photoresist, etching theelectroconductive polymer layer and finally stripping the non-developedphotoresist with an organic solvent, a patterned layer is obtained. Asimilar technique has been described in 1988 in Synthetic Metals, volume22, pages 265-271 for the design of an all-organic thin-film transistor.Such methods are cumbersome as they involve many steps and require theuse of hazardous chemicals.

OBJECTS OF THE INVENTION

[0012] It is an aspect of the present invention to provide a materialhaving a outermost layer that can be processed to an electroconductivepattern by a simple, convenient method which involves a low number ofsteps and which does not require the use of hazardous chemicals.

SUMMARY OF THE INVENTION

[0013] An electroconductive pattern can be realized with the materialsof the present invention, which are optionally conductivity enhanced, bypattern-wise exposure, with or without a subsequent single wetprocessing step, and optional conductivity enhancement. No etchingliquids or organic solvents are required.

[0014] The aspects of the present invention are realized by a materialfor making an electroconductive pattern, the material comprising asupport and a light-exposure differentiable element, characterized inthat the light-exposure differentiable element comprises an outermostlayer containing a polyanion and a polymer or copolymer of a substitutedor unsubstituted thiophene, and optionally a second layer contiguouswith the outermost layer; and wherein the outermost layer and/or theoptional second layer contains a light-sensitive component capable uponexposure of changing the removability of the exposed parts of theoutermost layer relative to the unexposed parts of the outermost layer.

[0015] These objects are also realized by a method of making anelectroconductive pattern on a support comprising the steps of:

[0016] providing a material as disclosed above;

[0017] image-wise exposing the material thereby obtaining adifferentiation of the removability, optionally with a developer, of theexposed and the non-exposed areas of the outermost layer;

[0018] processing the material, optionally with the developer, therebyremoving areas of the outermost layer; and

[0019] optionally treating the material to increase theelectroconductivity of the non-removed areas of the outermost layer.

[0020] These objects are also realized by a method of making anelectroconductive pattern on a support without a removal step comprisingthe steps of:

[0021] providing a material for making an electroconductive pattern,said material comprising a support and a light-exposure differentiableelement, characterized in that said light-exposure differentiableelement comprises an outermost layer containing a polyanion and apolymer or copolymer of a substituted or unsubstituted thiophene havinga surface resistivity lower than 10⁶ Ω/square, and optionally a secondlayer contiguous with the outermost layer; and wherein the outermostlayer and/or said optional second layer contains a bis(aryldiazosulfonate) compound according to formula (I):

MO₃S—N═N—Ar—L—Ar—N═N—SO₃M   (I)

[0022] where Ar is a substituted or unsubstituted aryl group, L is adivalent linking group, and M is a cation; capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer; and

[0023] image-wise exposing the material thereby obtaining reduction inthe conductivity of the exposed areas relative to non-exposed areas,optionally with a developer.

[0024] Further advantages and embodiments of the present invention willbecome apparent from the following description.

DETAILED DESCRIPTION OF THE INVENTION

[0025] Definitions

[0026] The term “support” means a “self-supporting material” so as todistinguish it from a “layer” which may be coated on a support, butwhich is itself not self-supporting. It also includes any treatmentnecessary for, or layer applied to aid, adhesion to the light-exposuredifferentiable element.

[0027] The term electroconductive means having a surface resistivitybelow 10⁶ Ω/square. Antistatic materials have surface resistivities inthe range from 10⁶ to 10¹¹ Ω/square and cannot be used as an electrode.

[0028] The term electroconductive pattern means a pattern made up by isthe non-removed areas of the outermost layer, according to the presentinvention, which are electroconductive or can be made electroconductiveby post-treatment.

[0029] Conductivity enhancement refers to a process in which theconductivity is enhanced e.g. by contact with high boiling point liquidssuch as di- or polyhydroxy- and/or carboxy groups or amide or lactamgroup containing organic compound optionally followed by heating atelevated temperature, preferably between 100 and 250° C., duringpreferably 1 to 90 seconds, results in conductivity increase.Alternatively in the case of aprotic compounds with a dielectricconstant ≧15, e.g. N-methyl-pyrrolidinone, temperatures below 100° C.can be used. Such conductivity enhancement is observed withpolythiophenes and can take place during the preparation of theoutermost layer or subsequently. Particularly preferred liquids for suchtreatment are N-methyl-pyrrolidinone and diethylene glycol such asdisclosed in EP-A 686 662 and EP-A 1 003 179.

[0030] The term removability as used in the description and claims ofthe present invention means mechanically removable in the absence of aliquid or removable with the application of a liquid with or without thesimultaneous or subsequent use of rubbing or other mechanical removalmeans. The application of liquid can dissolve, swell or disperse theoutermost layer according to the present invention such that removal isrealized or enabled.

[0031] The term light-exposure differentiable element means an elementwhich upon light exposure produces changes in the properties orcomposition of the exposed parts of the element with respect to theproperties or composition of the unexposed parts of the element.

[0032] The term multidiazonium salt includes all compounds with at leasttwo groups with two nitrogen atoms bonded together with a double ortriple bond, such groups including —N≡N⁺ and —N═N—R groups e.g.—N═N—SO₃M groups.

[0033] The term resin comprising a diazonium salt means a resin withgroups with two nitrogen atoms bonded together with a double or triplebond, such groups including —N≡N⁺ and —N═N—R groups e.g. —N═N—SO₃Mgroups.

[0034] In the case of removal of parts (areas) of the outermost layerafter pattern-wise exposure, the term surface resistivity ratio meansthe ratio of the surface resistivity of the parts (areas) of thelight-exposure differentiable element from which parts (areas) of theoutermost layer, according to the invention, have been removed to thatof the parts (areas) of the light-exposure differentiable element fromwhich no parts (areas) of the outermost layer, according to theinvention, have been removed, after treatment to enhance theconductivity of the non-removed parts (areas) of the outermost layer ifthis is required to increase (enhance) the conductivity of thenon-removed parts (areas) of the outermost layer.

[0035] In the case of non-removal of parts (areas) of the outermostlayer after pattern-wise exposure, the term surface resistivity ratiomeans the ratio of the surface resistivity of the exposed parts (areas)of the outermost layer to that of the non-exposed parts (areas) of theoutermost layer.

[0036] Material for making an electroconductive pattern

[0037] The material for making an electroconductive pattern, accordingto the present invention, need not itself be electroconductive as longas patterns produced with such a material can be renderedelectroconductive by a post-treatment process, such as a conductivityenhancement process. Furthermore, no material need be removed from theoutermost layer containing a polymer or copolymer of a substituted orunsubstituted thiophene, according to the present invention, in order torealize an electroconductive pattern, after optional processing toremove the residual light-sensitive component, as long as differentialremovability subsequent to exposure is feasible. In this case thelight-sensitive component present is capable upon exposure of realizingthis effect as well as changing the removability of the exposed parts ofthe outermost layer relative to the unexposed parts of the outermostlayer. The optional second layer must be between the outermost layer andthe support as it cannot be the outermost layer.

[0038] Electroconductive

[0039] The term “electroconductive” is related to the electricresistivity of the material. The electric resistivity of a layer isgenerally expressed in terms of surface resistivity R_(s) (unit Ω; oftenspecified as Ω/square). Alternatively, the electroconductivity may beexpressed in terms of volume resistivity R_(v)=R_(s)·d, wherein d is thethickness of the layer, volume conductivity k_(v)=1/R_(v) [unit:S(iemens)/cm] or surface conductivity k_(s)=1/R_(s) [unit:S(iemens).square].

[0040] All values of electric resistivity presented herein are measuredaccording to one of the following methods. In the first method thesupport coated with the electroconductive outermost layer is cut toobtain a strip having a length of 27.5 cm and a width of 35 mm and stripelectrodes are -applied over its width at a distance of 10 cmperpendicular to the edge of the strip. The electrodes are made of anelectroconductive polymer, ECCOCOAT CC-2 available from Emerson &Cumming Speciality polymers. Over the electrode a constant potential isapplied and the current flowing through the circuit is measured on apico-amperometer KEITHLEY 485. From the potential and the current,taking into account the geometry of the area between the electrodes, thesurface resistivity in Ω/square is calculated.

[0041] In the second method, the surface resistivity was measured bycontacting the outermost layer with parallel copper electrodes each 35mm long and 35 mm apart capable of forming line contacts, the electrodesbeing separated by a teflon insulator. This enables a direct measurementof the surface resistivity.

[0042] Support

[0043] Supports for use according to the present invention includepolymeric films, silicon, ceramics, oxides, glass, polymeric filmreinforced glass, glass/plastic laminates, metal/plastic laminates,paper and laminated paper, optionally treated, provided with a subbinglayer or other adhesion promoting means to aid adhesion to thelight-exposure differentiable element. Suitable polymeric films arepoly(ethylene terephthalate), poly(ethylene naphthalate), polystyrene,polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides,cellulosetriacetate, polyolefins and polyvinylchloride, optionallytreated by corona discharge or glow discharge or provided with a subbinglayer.

[0044] In the case of the realization of an electroconductive patternvia removal of exposed or non-exposed areas such treatment or subbinglayer should not hinder complete removal, whereas if theelectroconductive pattern can be realized without removal of exposed ornon-exposed areas such treatment should make removal of non-exposed orexposed areas more difficult.

[0045] In a first embodiment of the material according to the presentinvention the support is treated with a corona discharge or a glowdischarge. Both corona discharge and glow discharge enable the use ofpolymeric films as a support without a subbing layer. Such materials canbe developed, optionally while softly rubbing, and still yield anexcellent conductivity ratio between exposed and non-exposed areas.

[0046] Light-exposure differentiable element

[0047] A light-exposure differentiable element, according to the presentinvention, is an element which upon light exposure produces changes inthe properties or composition of the exposed parts of the element withrespect to the properties or composition of the unexposed parts of theelement. Examples of such changes are exposure-induced crosslinking;exposure-induced increase or decrease of solubility; andexposure-induced increase or decrease of adhesion to the support.

[0048] According to the present invention, these changes in theproperties or composition of the light-exposure differentiable elementare due to the presence of a light-sensitive component in the outermostlayer and/or the second layer, which enables either the exposed orunexposed parts of the outermost layer to be removed, optionally withthe assistance of a developer, i.e. the removability can either berendered more (positive working) or less (negative working) removable bya developer upon exposure to light.

[0049] In a second embodiment of the material according to the presentinvention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is amultidiazonium salt or a resin comprising a diazonium salt, whichreduces the removability of exposed parts of the outermost layer.Combinations of resins comprising a diazonium salt can also be used. Ifthe light-sensitive component is a multidiazonium salt or a resincomprising a diazonium salt, increasing the pH of the coatingdispersions and solutions used in preparing the light-exposuredifferentiable element has been found to improve the shelf-life, i.e.retention of properties upon storage, of materials according to thepresent invention. pH's between 2.5 and 9 are preferred, with pH'sbetween 3 and 6 being particularly preferred. Such pH's can, forexample, be realized by adding ammonium hydroxide.

[0050] In a third embodiment of the material according to the presentinvention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a quinonediazide compound, which increases the removability of exposed parts ofthe outermost layer.

[0051] In a fourth embodiment of the material according to the presentinvention the outermost layer has a surface resistivity lower than 10⁶Ω/square.

[0052] In a fifth embodiment of the material according to the presentinvention the outermost layer has a surface resistivity lower than 10⁴Ω/square.

[0053] In a sixth embodiment of the material according to the presentinvention the outermost layer has a surface resistivity capable of beinglower than 10⁶ Ω/square after treatment in a so-called conductivityenhancement process.

[0054] Polymer or copolymer of a substituted or unsubstituted thiophene

[0055] In a seventh embodiment of the material according to the presentinvention the polymer of a substituted or unsubstituted thiophenecorresponds to the formula (II):

[0056] in which n is larger than 1 and each of R¹ and R² independentlyrepresents hydrogen or an optionally substituted C₁₋₄ alkyl group ortogether represent an optionally substituted C₁₋₄ alkylene group or anoptionally substituted cycloalkylene group, preferably an ethylenegroup, an optionally alkyl-substituted methylene group, an optionallyC₁₋₁₂ alkyl- or phenyl-substituted ethylene group, a 1,3-propylene groupor a 1,2-cyclohexylene group.

[0057] The preparation of such a polythiophene and of aqueousdispersions containing such a polythiophene and a polyanion is describedin EP-A-440 957 and corresponding U.S. Pat. No. 5,300,575. Basically thepreparation of polythiophene proceeds in the presence of polymericpolyanion compounds by oxidative polymerisation of3,4-dialkoxythiophenes or 3,4-alkylenedioxythiophenes according to thefollowing formula:

[0058] wherein R¹ and R² are as defined above.

[0059] Stable aqueous polythiophene dispersions having a solids contentof 0.05 to 55% by weight and preferably of 0.1 to 10% by weight can beobtained by dissolving thiophenes corresponding to the formula above, apolyacid and an oxidising agent in an organic solvent or preferably inwater, optionally containing a certain amount of organic solvent, andthen stirring the resulting solution or emulsion at 0° C. to 100° C.until the polymerisation reaction is completed. The polythiophenesformed by the oxidative polymerisation are positively charged, thelocation and number of such positive charges being not determinable withcertainty and therefore not mentioned in the general formula of therepeating units of the polythiophene polymer.

[0060] The oxidising agents are those which are typically used for theoxidative polymerisation of pyrrole as described in for example J. Am.Soc. 85, 454 (1963). Preferred inexpensive and easy-to-handle oxidisingagents are iron(III) salts, e.g. FeCl₃, Fe(ClO₄)₃ and the iron(III)salts of organic acids and inorganic acids containing organic residues.Other suitable oxidising agents are H₂O₂, K₂Cr₂O₇, alkali or ammoniumpersulphates, alkali perborates, potassium permanganate and copper saltssuch as copper tetrafluoroborate. Air or oxygen can also be used asoxidising agents. Theoretically, 2.25 equivalents of oxidising agent permol of thiophene are required for the oxidative polymerisation thereof(J. Polym. Sci. Part A, Polymer Chemistry, Vol. 26, p.1287, 1988). Inpractice, however, the oxidising agent is used in excess, for example,in excess of 0.1 to 2 equivalents per mol of thiophene.

[0061] Polyanion

[0062] The polyacid forms a polyanion or, alternatively, the polyanioncan be added as a salt of the corresponding polyacids, e.g. an alkalisalt. Preferred polyacids or salts thereof are polymeric carboxylicacids such as poly(acrylic acid), poly((meth)acrylic acid) andpoly(maleic acid) or polymeric sulphonic acids such as poly(styrenesulphonic acid) or poly(vinyl sulphonic acid). Alternatively, copolymersof such carboxylic and/or sulphonic acids and of other polymerizablemonomers such as styrene or acrylates can be used.

[0063] In an eighth embodiment of the material according to the presentinvention the polyanion is poly(styrene sulphonate).

[0064] The molecular weight of these polyanion forming polyacids ispreferably between 1000 and 2×10⁶, more preferably between 2000 and 5×10⁵. These polyacids or their alkali salts are commercially available andcan be prepared according to the known methods, e.g. as described inHouben-Weyl, Methoden der Organische Chemie, Bd. E20 MakromolekulareStoffe, Teil 2, (1987), pp. 1141.

[0065] Dispersion of a polyanion and a polymer or copolymer of asubstituted or unsubstituted thiophene

[0066] The coating dispersion or solution of a polyanion and a polymeror copolymer of a substituted or unsubstituted thiophene can alsocomprise additional ingredients, such as one or more binders, one ormore surfactants, spacing particles, UV-acutance compounds orIR-absorbers.

[0067] Anionic and non-ionic surfactants are preferred. Suitablesurfactants include ZONYL™ FSN 100 and ZONYL™ FSO 100, an ethoxylatednon-ionic fluoro-surfactant with the structure:F(CF₂CF₂)_(y)CH₂CH₂O(CH₂CH₂O)_(x)H, where x=0 to ca. 15 and y=1 to ca.7, both from Du Pont.

[0068] The coating dispersion or solution of a polyanion and a polymeror copolymer of a substituted or unsubstituted thiophene preferably alsocomprises an organic compound that is: a linear, branched or cyclicaliphatic C₂₋₂₀ hydrocarbon or an optionally substituted aromatic C₆₋₁₄hydrocarbon or a pyran or a furan, the organic compound comprising atleast two hydroxy groups or at least one —COX or —CONYZ group wherein Xdenotes —OH and Y and Z independently of one another represent H oralkyl; or a heterocyclic compound containing at least one lactam group.Examples of such organic compounds are e.g. N-methyl-2-pyrrolidinone,2-pyrrolidinone, 1,3-dimethyl-2-imidazolidone,N,N,N′,N′-tetramethylurea, formamide, dimethylformamide, andN,N-dimethylacetamide. Preferred examples are sugar or sugar derivativessuch as arabinose, saccharose, glucose, fructose and lactose, or di- orpolyalcohols such as sorbitol, xylitol, mannitol, mannose, galactose,sorbose, gluconic acid, ethylene glycol, di- or tri(ethylene glycol),1,1,1-trimethylol-propane, 1,3-propanediol, 1,5-pentanediol,1,2,3-propantriol, 1,2,4-butantriol, 1,2,6-hexantriol, or aromatic di-or polyalcohols such as resorcinol.

[0069] Multidiazonium salts

[0070] A multidiazonium salt is a salt with at least two groups with twonitrogen atoms bonded together with a double or triple bond, such groupsincluding —N≡N⁺ and —N═N—R groups, e.g. —N═N—SO₃M groups e.g.bisdiazonium salts, trisdiazonium salts, tetrakisdiazonium salts,bis(aryldiazosulphonate) salts, tris(aryldiazosulphonate) salt andterakis(bis(aryldiazosulphonate) salts.

[0071] Upon exposure the light-exposure differentiable elementcontaining a multidiazonium salt is converted from water removable towater unremovable (due to the destruction of the diazonium groups) andadditionally the photolysis products of the diazo may increase the levelof crosslinking of the polymeric binder or resin comprising amultidiazonium salt if present, thereby selectively converting thesurface, into an image pattern, from removable to unremovable. Theunexposed areas remain unchanged, i.e. removable. Combinations ofmultidiazonium salts can also be used.

[0072] Bisdiazonium salts for use in the present invention include:benzidine tetrazoniumchloride, 3,3′-dimethylbenzidinetetrazoniumchloride, 3,3′-dimethoxybenzidine tetrazoniumchloride,4,4′-diaminodiphenylamine tetrazoniumchloride, 3,3′-diethylbenzidinetetrazoniumsulphate, 4-aminodiphenylamine diazoniumsulphate,4-aminodiphenylamine diazoniumchloride, 4-piperidino anilinediazoniumsulphate, 4-diethylamino aniline diazoniumsulphate andoligomeric condensation products of diazodiphenylamine and formaldehyde.

[0073] In a ninth embodiment of the material according to the presentinvention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is abis(aryldiazosulphonate) salt, a tris(aryldiazosulphonate) salt or atetrakis(aryldiazosulphonate) salt, which reduces the removability ofexposed parts of the outermost layer.

[0074] In an tenth embodiment of the material according to the presentinvention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer, according to formula (I):

MO₃S—N═N—Ar—L—Ar—N═N—SO₃M   (I)

[0075] where Ar is a substituted or unsubstituted aryl group, L is adivalent linking group, and M is a cation. L preferably represents asubstituted or unsubstituted divalent aryl group or a substituted orunsubstituted saturated or unsaturated alkylene group, whose chain isoptionally substituted with at least one of an oxygen atom, a sulphuratom or a nitrogen atom. Ar preferably represents an unsubstitutedphenyl group or a phenyl group substituted with one or more alkylgroups, aryl groups, alkoxy groups, aryloxy groups or amino groups. Mpreferably represents a cation such as NH₄ ⁺ or a metal ion such as acation of Al, Cu, Zn, an alkaline earth metal or alkali metal.

[0076] Particularly suitable bis(aryldiazosulphonate) salts, accordingto the present invention, are: absorption of a 25 ppm λ_(max) solution[nm] in water BADS01 308 0.785

BADS02 308 1.568

BADS03 —

[0077] In an eleventh embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer, is selected from the group consisting ofBADS01, BADS02 and BADS03.

[0078] In a first embodiment of the method of making anelectroconductive pattern on a support without a removal step, accordingto the present invention, the aryldiazosulfonate according to formula(I) is selected from the group consisting of BADS01, BADS02 and BADS03.

[0079] Resins comprising a diazonium salt

[0080] The term resin comprising a diazonium salt means a resin withgroups with two nitrogen atoms bonded together with a double or triplebond, such groups including —N≡N⁺ and —N═N—R groups e.g. —N═N—SO₃Mgroups. Suitable resins comprising a diazonium salt, according to thepresent invention, include polymers or copolymers of anaryldiazosulphonate and condensation products of an aromatic diazoniumsalt. Such condensation products are described, for example, in DE-P-1214 086.

[0081] Upon exposure the light-exposure differentiable elementcontaining resins comprising a diazonium salt are converted fromremovable to unremovable (due to the destruction of the diazoniumgroups) and additionally the photolysis products of the diazo mayincrease the level of crosslinking of the polymeric binder or resincomprising a diazonium salt, thereby selectively converting the surface,into an image pattern, from removable to unremovable. The unexposedareas remain unchanged, i.e. removable.

[0082] In a twelfth embodiment of the material according to the presentinvention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a polymer orcopolymer of an aryldiazosulphonate, which reduces the removability ofexposed parts of the outermost layer.

[0083] In a thirteenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a polymer orcopolymer of an aryldiazosulphonate, which reduces the removability ofexposed parts of the outermost layer, represented by formula (III):

[0084] wherein R⁰, R¹ and R² each independently represent hydrogen, analkyl group, a nitrile or a halogen, e.g. Cl, L represents a divalentlinking group, n represents 0 or 1, A represents an aryl group and Mrepresents a cation. L preferably represents divalent linking groupselected from the group consisting of: —(X)_(t)-CONR³—, —(X)_(t)-COO—,—X— and —(X)_(t)-CO—, wherein t represents 0 or 1; R³ representshydrogen, an alkyl group or an aryl group; X represents an alkylenegroup, an arylene group, an alkylenoxy group, an arylenoxy group, analkylenethio group, an arylenethio group, an alkylenamino group, anarylenamino group, oxygen, sulphur or an aminogroup. A preferablyrepresents an unsubstituted aryl group, e.g. an unsubstituted phenylgroup or an aryl group, e.g. phenyl, substituted with one or more alkylgroups, aryl groups, alkoxy groups, aryloxy groups or amino groups. Mpreferably represents a cation such as NH⁴ ⁺ or a metal ion such as acation of Al, Cu, Zn, an alkaline earth metal or alkali metal.

[0085] Polymers and copolymers of an aryldiazosulphonate can be preparedby homo- or copolymerization of aryldiazosulphonate monomers with otheraryldiazosulphonate monomers and/or with vinyl monomers such as(meth)acrylic acid or esters thereof, (meth)acrylamide, acrylonitrile,vinylacetate, vinylchloride, vinylidene chloride, styrene, alpha-methylstyrene etc. A particularly preferred comonomer ishydroxyethylmethacrylate. Suitable aryldiazosulphonate monomers forpreparing such polymers and copolymers of an aryldiazosulphonate, asused in the present invention, are: ADS-MONOMER 01

ADS-MONOMER 02

ADS-MONOMER 03

ADS-MONOMER 04

ADS-MONOMER 05

ADS-MONOMER 06

ADS-MONOMER 07

[0086] Specific examples of suitable aryldiazosulphonate polymers aredescribed in EP-A-771 645.

[0087] Suitable resins comprising a diazonium salt, according to thepresent invention, are given below. In the case of polymers andcopolymers of an aryldiazosulphonate, the respective monomer ratios areexpressed as percentages by weight. NDP01 = Negalux N18, a diphenylaminediazonium resin from PCAS NDP02 = diazo resin No. 8 from FAIRMOUNTCHEMICAL NDP03 = methyl methacrylate, ADS-MONOMER 01 (82/18) copolymerNDP04 = homopolymer of ADS-MONOMER 01 NDP05 = hydroxyethylacrylate,ADS-MONOMER 01 (80/20) copolymer NDP06 = methyl methacrylate,ADS-MONOMER 01 (80/20) copolymer NDP07 = N-isopropyl-acrylamide,ADS-MONOMER 01 (80/20) copolymer NDP08 = N-isopropyl-acrylamide,ADS-MONOMER 0l (85/15) copolymer NDP09 = N-t-butyl-acrylamide,ADS-MONOMER 01 (75/25) copolymer NDP10 = N-t-butyl-acrylamide,ADS-MONOMER 01 (70/30) copolymer NDP11 = hydroxyethyl methacrylate,2-propenoic acid, 2-methyl-,2-[{[(2-nitrophenyl)methoxy]carbonyl}amino]ethyl ester, ADS- MONOMER 01(85/10/5) terpolymer NDP12 = hydroxyethyl methacrylate, ADS-MONOMER 01(95/5) copolymer NDP13 = hydroxyethyl methacrylate, ADS-MONOMER 01(97/3) copolymer NDP14 = hydroxyethyl methacrylate, ADS-MONOMER 01(90/10) copolymer NDP15 = hydroxyethyl methacrylate, ADS-MONOMER 01(80/20) copolymer NDP16 = methyl methacrylate, ADS-MONOMER 01 (40/60)copolymer NDP17 = methyl methacrylate, ADS-MONOMER 01 (60/40) copolymerNDP18 = phenyl methacrylate, ADS-MONOMER 01 (40/60) copolymer NDP19 =3-methacryloxypropyltriisopropylsilane, methyl methacrylate, ADS-MONOMER01 (10/70/20) copolymer NDP20 = 2-propenoic acid 2-phosphonooxy)ethylester, methyl methacrylate, ADS-MONOMER 01 (2/80/18) copolymer NDP21 =acrylic acid, ADS-MONOMER 01 (80/20) copolymer NDP22 =4-(2-acryloyloxyethoxy)phenyl 2-hydroxy-2-propyl ketone, methylmethacrylate, ADS-MONOMER 01 (10/70/20) copolymer NDP23 = acrylonitrile,methyl methacrylate, ADS-MONOMER 01 (10/70/20) copolymer NDP24 =ADS-MONOMER 06, methyl methacrylate, ADS-MONOMER 01 (5/80/15) copolymerNDP25 = ADS-MONOMER 07, methyl methacrylate, ADS-MONOMER 01 (3/82/15)copolymer NDP26 = methyl methacrylate, ADS-MONOMER 02 (80/20) copolymerNDP27 = methyl methacrylate, ADS-MONOMER 03 (80/20) copolymer NDP28 =methyl methacrylate, ADS-MONOMER 05 (75/25) copolymer NDP29 = methylmethacrylate, ADS-MONOMER 04 (80/20) copolymer NDP30 = methylmethacrylate, ADS-MONOMER 01 (ammonium salt) (80/20) copolymer NDP31 =methyl methacrylate, ADS-MONOMER 01 (tetramethylammonium salt) (80/20)copolymer NDP32 = methyl methacrylate, ADS-MONOMER 01(tetraethylammonium salt) (80/20) copolymer NDP33 = hydroxyethylmethacrylate, ADS-MONOMER 01 (85/15) copolymer NDP34 = condensationproduct of 4-diazodiphenylamine sulphate and formaldehyde NDP35 =condensation product of 4-diazodiphenylamine toluene sulphonate andformaldehyde NDP36 = condensation product of 4-diazodiphenylaminetetrafluoroborate and formaldehyde

[0088] In a fourteenth embodiment of the material according to thepresent invention in the light-exposure differentiable element theweight ratio of the polymer or copolymer of an aryldiazosulphonate tothe polymer or copolymer of a substituted or unsubstituted thiophene isbetween 10:200 and 400:200.

[0089] Combination of a multidiazonium salt and a resin comprising adiazonium salt

[0090] In a fifteenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a combinationof a resin comprising an aryldiazosulphonate, which reduces theremovability of exposed parts of the outermost layer, and abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer.

[0091] In a sixteenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a combinationof a resin comprising an aryldiazosulphonate, which reduces theremovability of exposed parts of the outermost layer, and abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer, in the weight percentage ratio range of60%/40% to 10%/90%.

[0092] In a seventeenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a combinationof a resin comprising an aryldiazosulphonate, which reduces theremovability of exposed parts of the outermost layer, and abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer, in the weight percentage ratio range of50%/50% to 20%/80%.

[0093] In an eighteenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is a combinationof a copolymer of hydroxyethylmethacrylate andsodium-4-methacryloyl-aminophenyl-diazo-sulphonate, which reduces theremovability of exposed parts of the outermost layer, and anbis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of the outermost layer.

[0094] Quinone diazide compounds

[0095] In a nineteenth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is aquinonediazide compound, which increases the removability of exposedparts of the outermost layer.

[0096] In a twentieth embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is ano-quinone-diazide compound (NQD), which increases the removability ofexposed parts of the outermost layer.

[0097] Particularly preferred o-quinone-diazide compounds areo-naphthoquinonediazidosulphonic acid esters or o-naphthoquinonediazidocarboxylic acid esters of various hydroxyl compounds ando-naphthoquinonediazidosulphonic acid amides oro-naphthoquinonediazidocarboxylic acid amides of various aromatic aminecompounds.

[0098] Two variants of NQD systems can be used: one-component systemsand two-component systems. In the former case, the sulphonic or carboxylacid group is linked directly to the phenolic hydroxy group of a waterinsoluble, alkali soluble or swellable resin having a phenolic hydroxygroup. It is preferred that some phenolic hydroxy groups remainunsubstituted. Examples of such compounds include phenol, cresol,resorcinol and pyrogallol. Examples of preferred water insoluble, alkalisoluble or swellable resins having a phenolic hydroxy group includephenol-formaldehyde resin, cresol-formaldehyde resin, pyrogallol-acetoneresin and resorcinol-benzaldehyde resin. Typical examples include estersof napthoquinone-(1,2)-diazidosulphonic acid and phenol-formaldehyderesin or cresol-formaldehyde resin, esters ofnaphthoquinone-(1,2)-diazido-(2)-5-sulphonic acid and pyrogallol-acetoneresin as disclosed in U.S. Pat. No. 3,635,709 and esters ofnaphthoquinone-(1,2)-diazido-(2)-5-sulphonic acid andresorcinol-pyrogallol-acetone copolycondensates as disclosed in JP KOKAINo. Sho 55-76346.

[0099] Examples of other useful compounds are polyesters having hydroxylgroups at their termini esterified with o-naphthoquinonediazidesulphonylchloride as disclosed in JP KOKAI No. Sho 50-117503; homopolymers ofp-hydroxystyrene or copolymers thereof with other copolymerizablemonomers esterified with o-naphthoquinonediazidosulphonyl chloride asdisclosed in JP KOKAI No. Sho 50-113305; condensates of alkylacrylate-acryloyloxyalkyl carbonate-hydroxyalkyl acrylate copolymerswith o-naphthoquinonediazidosulphonyl chloride as disclosed in U.S. Pat.No. 3,859,099; amides of copolymers of p-aminostyrene and monomerscopolymerizable therewith and o-naphthoquinonediazido-sulphonic acid oro-naphthoquinonediazidocarboxylic acid as disclosed in U.S. Pat. No.3,759,711; as well as ester compounds of polyhydroxybenzophenone ando-naphthoquinonediazidosulphonyl chloride.

[0100] In a twenty-first embodiment of the material according to thepresent invention the light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of the outermost layerrelative to the unexposed parts of the outermost layer is ano-quinone-diazide compound (PQD), which increases the removability ofexposed parts of the outermost layer, and the light-exposuredifferentiable element further contains an alkali soluble resin.

[0101] Particularly suitable quinonediazide compounds according to thepresent invention are: PQD01 = AZ 7217, a positive working photoresistfrom CLARIANT PQD02 = 2-diazo-1-naphthol-5-sulfonic acid sodium saltPQD03 = 1-diazo-2-naphthol-4-sulfonic acid sodium salt PQD04 =2-diazo-1-naphthol-5-(4′-methyl-phenylsulphonate) PQD05 =2-diazo-1-naphthol-5-phenylsulphonate PQD06 =bis(6′-diazo-5′-oxy-5′-sulphonate naphthalene)-2,4- benzophenone PQD07 =2-diazo-1-oxy-(2′-benzotriazolyl-4′-methyl-phenyl)-5- sulphonatenaphthalene PQD08 = partial esterification product of 1,2-naphthoquinone(2) diazide-5-sulfonyl chloride and a p-t-butylphenol- formaldehydecopolymer PQD09 = partial esterification product of 1,2-naphthoquinonediazide-5-sulfonyl chloride and a cresol formaldehyde polymer PQD10 =partial esterification product of 1,2-naphthoquinone (2)diazide-5-sulfonylchloride and a p-cresol-formaldehyde resin PQD11 =partial esterification product of 1,2-naphthoquinone (2)diazide-5-sulfonyl chloride and a p-t-butylphenol- formaldehydecopolymer

[0102] Binders

[0103] In the materials for making an electroconductive pattern,according to the present invention, the light-exposure differentiableelement contains a binder.

[0104] In a twenty-second embodiment of the material according to thepresent invention the outermost layer contains a binder, e.g. polyvinylalcohol and a vinylidene chloride, methyl methacrylate, itaconic acid(88/10/2) terpolymer, if the light-sensitive component capable uponexposure of changing the removability of the exposed parts of theoutermost layer relative to the unexposed parts of the outermost layeris present in the outermost layer.

[0105] In a twenty-third embodiment of the material according to thepresent invention the optional second layer contains a binder, e.g.polyvinyl alcohol and a hydroxyethyl methacrylate copolymer, if thelight-sensitive component capable upon exposure of changing theremovability of the exposed parts of the outermost layer relative to theunexposed parts of the outermost layer is present in the second layer.

[0106] Suitable binders for use in the present invention are describedin EP-A 564 911 and include water-soluble polymers, such as poly(vinylalcohol), water-soluble homo- and co-polymers of acrylic acid and homo-and co-polymers of methacrylic acid, and polymer latexes. Preferredbinders include poly(vinyl alcohol) and homo- and co-polymers ofhydroxyethyl methacrylate and copolymers of 2-propenoic acid2-phosphonooxy)ethyl ester, copolymers of 2-methyl-2-propenoic acid2-phosphonooxy)ethyl ester. Such binders may be treated with a hardeningagent, e.g. an epoxysilane such as 3-glycidyloxypropyltrimethoxysilaneas described in EP-A 564 911, which is especially suitable when coatingon a glass substrate.

[0107] In the application of NQD as two-component systems variouslow-molecular NQD sulphonic or carboxyl acid derivatives are dissolvedmainly in certain water insoluble, alkali soluble or swellable resins;the latter acts as polymeric binder for NQD. Preferably the 4- or5-sulphonyl or carboxyl substituted 1,2 naphthoquinonediazides areesters of 1,2 naphthoquinonediazides-4- or -5-sulphonic or carboxylicacids with a phenolic compound having at least two phenolic hydroxygroups, more preferably with a phenolic compound having at least threephenolic hydroxy groups. Further suitable 1,2 naphthoquinone-2-diazidesare disclosed in GB-A 739654 and in U.S. Pat. No. 4,266,001. Preferredwater insoluble, alkali soluble or swellable resins are resins, whichcomprise phenolic hydroxy groups, oxime groups or sulphonamido groups.More preferred are resins having phenolic hydroxy groups, and phenolichydroxy functionalized derivatives of poly(meth)acrylates, which can besynthesised starting from e.g. hydroxyethyl(meth)acrylate. Mostpreferred are synthetic novolac resins and typical examples thereof arephenolformaldehyde resin, cresol-formaldehyde resin, andphenol-cresol-formaldehyde copolycondensed resins as disclosed in JPKOKAI No. Sho 55-57841.

[0108] Exposure process

[0109] The material of the present invention can be image-wise exposedto ultraviolet light optionally in combination with blue light in thewavelength range of 250 to 500 nm or infrared light. Upon image-wiseexposure, a differentiation of the removability with a developer of theexposed and non-exposed areas is induced. Useful exposure sources arehigh or medium pressure halogen mercury vapour lamps, e.g. of 1000 W orlasers having an emission wavelength in the range from about 700 toabout 1500 nm, such as a semiconductor laser diode, a Nd:YAG laser or aNd:YLF laser.

[0110] Development process

[0111] After the image-wise exposure the material is developed in adeveloper which can be deionized water or is preferably water-based.During development the exposed (positive working) or non-exposed(negative working) areas together with the electroconductive polymer areremoved and an electroconductive pattern is thereby obtained. Suitableaqueous developers are deionized water, AZ303 (Clariant) or EN232(AGFA-GEVAERT N.V.). When a subbing layer (also called substrate layer)is present on the support the material is preferably rubbed thoroughlywith a tissue during development to avoid residual conductivity. Therubbing can be done in the processing fluid or in a separate water bathafter the development stage. Equal results can be obtained by applying ahigh pressure water jet after the development stage, thereby avoidingcontact with the conductive areas. Alternatively, if conductivityenhancement is necessary, the developer can contain the conductivityenhancement agent, thereby combining the steps of development andcontact with the conductivity enhancement agent.

[0112] While the present invention will hereinafter be described inconnection with preferred embodiments thereof, it will be understoodthat it is not intended to limit the invention to those embodiments. Allpercentages given in the EXAMPLES are percentages by weight unlessotherwise stated.

EXAMPLES

[0113] Ingredients used in the light-exposure differentiable elementwhich are not mentioned above:

[0114] PEDOT=poly(3,4-ethylenedioxythiophene)

[0115] PSS=polystyrene sulphonic acid)

[0116] LATEX01=vinylidene chloride, methyl methacrylate, itaconic acid(88/10/2) terpolymer, available as 30% aqueous dispersion

[0117] Z6040=3-glycidoxypropyltrimethoxysilane from DOW CORNING

[0118] ZONYL™FSO 100=an ethoxylated non-ionic fluoro-surfactant with thestructure: F(CF₂CF₂)_(y)CH₂CH₂O(CH₂CH₂O)_(x)H, where x=0 to ca. 15 andy=1 to ca. 7 from Du Pont

[0119] Ingredients used in the subbing layers:

[0120] =a copolyester of 26.5 mol % terephthalic acid, 20

[0121] LATEX02=mol % isophthalic acid, 3.5 mol % 5-sulphoisophthalicacid and 50 mol % ethylene glycol available as a 20% aqueous dispersion;

[0122] LATEX03=a copolymer of 80% ethyl acrylate and 20% methacrylicacid available as a 27% aqueous dispersion;

[0123] LATEX04=a copolymer of 49% methyl methacrylate, 49% of butadieneand 2% itaconic acid;

[0124] KIESELSOL 100F=a colloid silica from BAYER, available as a 30%aqueous dispersion;

[0125] KIESELSOL 300F=a colloidal silica from BAYER, available as a 30%aqueous dispersion;

[0126] ARKOPON™ T=a sodium salt of N-methyl-N-2-sulfoethyloleylamide byHOECHST a surfactant from HOECHST, supplied as a 40% concentrate;

[0127] MERSOLAT™H76=a sodium pentadecylsulfonate by BAYER, supplied as a76% concentrate;

[0128] ULTRAVON™ W=a sodium arylsulfonate from CIBA-GEIGY, supplied as a75-85% concentrate;

[0129] ARKOPAL™ N060=a nonylphenylpolyethylene-glycol from HOECHST;

[0130] HORDAMER™ PE02=polyethylene from HOECHST, available as a 40%aqueous dispersion;

[0131] PAREZ RESIN™=melamine-formaldehyde resin from AMERICAN CYANAMID613 available as 80% solids;

[0132] The following supports based on 100 μm polyethylene terephthalatefilm were used in the EXAMPLES: Support nr. Composition 01 subbing layerconsisting of 79.1% LATEX01; 18.6% KIESELSOL ™ 100F; 0.5% MERSOLAT ™ H;and 1.9% ULTRAVON ™ W 02 surface treated with a corona discharge 03surface treated with an glow discharge 04 subbing layer consisting of afirst layer of 79.1% LATEX0l; 18.6% KIESELSOL ™ 100F; 0.5% MERSOLAT ™ H;and 1.9% ULTRAVON ™ W; and an outermost layer consisting of 49% gelatin,44% KIESELSOL ™ 300F, 1.72% ULTRAVON ™ W, 0.86% ARKOPAL ™ N060, 2.86%hexylene glycol, 1.43% trimethylol propane and 0.13% polymethylmethacylate, a 3 μm matting agent. 05 subbing layer consisting of 77.2%of LATEX02; 5.8% of LATEX03; 1.3% HORDAMER ™ PE02 and 14.6% PAREZRESIN ™ 613. 06 subbing layer consisting of a first layer of 85.6% ofLATEX0l, 9.5% of KTESELSOL ™ 100F, 2.5% of PEDOT/PSS, 0.5% of MERSOLAT ™76H and 1.9% ULTRAVON ™ W; and an outermost layer consisting of 49%gelatin, 44% KIESELSOL ™ 300F, 1.72% ULTRAVON ™ W, 0.86% ARKOPAL ™ N060,2.86% 2-methyl-2,4-pentanediol, 1.43% trimethylol propane and 0.13%polymethyl methacylate 3 μm matting agent. 07 subbing layer consistingof 79.8% LATEX02; 19.9% KIESELSOL ™ 100F; and 0.3% ARKOPON ™ T 08subbing layer consisting of 75.0% LATEX01, 9.0% LATEX03 and 16.0%KIESELSOL ™ 100F

[0133] For the corona discharge treatment of polyethylene terephthalatefilm in air, an AHLBRANDT™ corona treater type 53-02 was used consistingof 2 quartz electrodes, a grounded treater roll and a 15 kHz generator.The air gap between the electrode and film was 1.2 mm and the film wasendowed with optimal adhesion properties by transporting it at a speedof 10 m/min under the corona treater at a watt density of 400 Wmin/m².

[0134] The glow discharge treatment of polyethylene terephthalate filmwas carried out in a vacuum system consisting of a reactor vessel,vacuum pumps, a gas inlet, a DC power source and a titanium glowcathode. The operating conditions used were a transport speed of 40m/min, an air pressure of 10⁻² mbar and a power density of 40 Wmin/m²and a distance between the cathode and film of 100 mm.

[0135] poly(3,4-ethylenedioxythiophene)/poly(styrene sulphonate)[PEDOT/PSS] dispersion

[0136] The aqueous dispersions of PEDOT/PSS in a weight ratio of 1:2.4used in the EXAMPLES were prepared according to the method described inEP-A-1 079 397. The particle size of the PEDOT/PSS latex was determinedby CPS disc centrifuge measurements to be narrow with a maximum at 25 nmwith an average particle size of 30-50 nm.

EXAMPLE 1

[0137] In EXAMPLE 1, a negative working light-sensitive compound wasused for patterning a polythiophene outermost layer. Support nr. 1 wascoated on the subbed side with 40 mL/m² (40 μm wet thickness) of thecoating dispersion given in Table 1. The compositions of the driedoutermost layers are also given in Table 1. TABLE 1 SAMPLE INGREDIENT[g] I (COMP) II III IV V VI VII 1.2% aqueous dispersion of PEDOT/PSS 417417 417 417 417 417 417 0.25% aqueous solution of NDP01 — 100 250 500 —— — 0.25% aqueous solution of NDP02 — — — — 100 250 500 LATEX01 3.3 — —— — — — 2% aqueous solution of ZONYL ™ FSO 100 10 10 10 10 10 10 10N-methyl-pyrrolidinone 50 50 50 50 50 50 50 deionized water 514.7 423273 23 423 423 423 COVERAGE [mg/m²] PEDOT/PSS 200 200 200 200 200 200200 NDP01 — 10 25 50 — — — NDP02 — — — — 10 25 50 LATEX01 100 — — — — —— ZONYL ™ FSO 100 8 8 8 8 8 8 8

[0138] The Samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 30-75s at 2 mW/cm²(=exposure of 0.06-0.15 J/cm ²) and processed with deionized water. Theresults are given in Table 2. TABLE 2 SAMPLE PROPERTY I (COMP) II III IVV VI VII R_(s) differentiation between no yes yes yes yes yes yesexposed and non-exposed areas after processing R_(s) (Ω/square) ofcoated layer 730 760 650 980 490 620 1500 before patterning R_(s)(Ω/square) of the non- — 5 × 10⁴ 5 × 10⁴ 5 × 10⁴ 5 × 10⁴ 5 × 10⁴ 5 × 10⁴exposed areas after exposure and processing R_(s) (Ω/square) of the non-— >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ exposed areas after exposure andthorough rubbing during processing R_(s) (Ω/square) of the exposed 730850 650 960 480 630 1500 areas after exposure and processing

[0139] The results in Table 2 show that for the samples II to VIIaccording to the invention, structured conducting PEDOT/PSS-containingoutermost layers were obtained and that the patterning method ofexposure and developing does not substantially affect the conductivityof the outermost layer. After processing the surface a resistivity ofthe non-exposed areas was above 10⁴ Ω/square. A surface resistivity inthe non-exposed areas above 10¹⁰ Ω/square could be obtained when thematerial was rubbed thoroughly with a tissue during processing.

EXAMPLE 2

[0140] In EXAMPLE 2, a negative working light-sensitive compound wasused for patterning a polythiophene outermost layer. Support nr. 1 wascoated on the subbed side with 40 mL/m² (40 μm wet thickness) of thecoating dispersions given in Table 3 and dried giving the compositionsgiven in Table 3. TABLE 3 composition of the coating dispersions SAMPLEINGREDIENT [g] VIII (COMP) IX X XI XII XIII XIV 1.2% aq. PEDOT/PSSdispersion 417 417 417 417 417 417 417 17% solution of NDP03 in — 1.53.7 7.1 14.2 28.4 56.8 isopropanol/water (60/40) LATEX01 8.3 — — — — — —2% aq. sol. ZONYL ™ FSO 100 10 10 10 10 10 10 10 N-methyl-pyrrolidinone50 50 50 50 50 50 50 deionized water 514.7 522 519 516 509 495 466COVERAGE PEDOT/PSS [mg/m²] 200 200 200 200 200 200 200 NDP03 [mg/m²] —10 25 50 100 200 400 LATEX01 [mg/m²] 100 — — — — — — ZONYL ™ FSO 100 8 88 8 8 8 8

[0141] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 250s at 2 mW/cm²(=exposure of 0.5 J/cm²) and processed in water while rubbing with atissue under water and the results are presented in Table 4. TABLE 4property VIII (COMP) IX X XI XII XIII XIV R_(s) differentiation betweenno yes yes yes yes yes yes exposed and non-exposed areas afterprocessing R_(s) (Ω/square) of coated 760  689  739  790 1100 1600  5500layer before patterning R_(s) (Ω/square) of the non- — >10⁵ >10⁵ >10⁵>10⁵ >10⁵ >10⁵ exposed areas after exposure and processing R_(s)(Ω/square) of the non- — >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ >10¹⁰ exposedareas after exposure and thorough rubbing during processing R_(s)(Ω/square) of exposed 760 1344 1375 1360 2100 2400 22000 areas afterexposure and processing

[0142] The results in Table 4 show that in the samples IX to XIVaccording to the invention structured conducting PEDOT/PSS-containingoutermost layers were obtained. After processing the surface resistivityof the non-exposed areas was above 10⁵ Ω/square. A surface resistivityin the non-exposed areas above 10¹⁰ Ω/square could be obtained when thematerial was rubbed thoroughly with a tissue during processing.

EXAMPLE 3

[0143] In EXAMPLE 3, NDP04, a homopolymer of ADS-MONOMER 01 wasincorporated into the PEDOT/PSS-containing outermost layer to realizepatterning of a polythiophene outermost layer. Samples XV to XXIV wereproduced by coating 40 mL/m² of the dispersions given in Table 5 onSupport nr. 1 to 8 to a wet thickness of 40 μm. After drying the SamplesXV to XXIV had the compositions also given in Table 5. TABLE 5composition of the coating dispersions SAMPLE INGREDIENT [g] XV XVI XVIIXVIII XIX XX XXI XXII XXIII XXIV Support nr. 1 1 1 2 3 4 5 6 7 8 1.2%aqueous dispersion 417 417 417 417 417 417 417 417 417 417 of PEDOT/PSS17.8% aq. sol. of NDP04 7 14 21 14 14 14 14 14 14 14 2% aqueous solutionof 10 10 10 10 10 10 10 10 10 10 ZONYL ™ FSO 100 N-methyl-pyrrolidinone50 50 50 50 50 50 50 50 50 50 deionized water 516 509 502 509 509 509509 509 509 509 COVERAGE PEDOT/PSS [mg/m²] 200 200 200 200 200 200 200200 200 200 NDP04 [mg/m²] 50 100 150 100 100 100 100 100 100 100 ZONYLFSO 100 [mg/m²] 8 8 8 8 8 8 8 8 8 8

[0144] The Samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 200s at 2 mW/cm²(=exposure of 0.4 J/cm²) and processed in water (softly rubbing with atissue under water). The results are given in Table 6. TABLE 6 SAMPLEPROPERTY XV XVI XVII XVIII XIX XX XXI XXII XXIII XXIV Support nr 1 1 1 23 4 5 6 7 8 R_(s) (Ω/square) of 1.7 × 10³ 5.2 × 10³ 1.5 × 10⁴ 3.8 × 10³ 3.8 × 10³  1.8 × 10⁵ 4.1 × 10³  2.5 × 10⁵ 4.0 × 10³ 9.7 × 10³ coatedlayer before patterning R_(s) (Ω/square) of 2.4 × 10⁵ 4.2 × 10⁵ 6.3 ×10⁵ 6.5 × 10¹² 6.2 × 10¹² 9.9 × 10⁸ 3.8 × 10¹² 9.0 × 10⁶ 9.6 × 10⁵ 1.1 ×10⁵ non-exposed areas after exposure and processing R_(s) (Ω/square) of— 7.2 × 10³ — 5.6 × 10³  6.1 × 10³  2.4 × 10⁵ 6.1 × 10³  3.4 × 10⁵ 6.9 ×10³ 2.2 × 10⁴ exposed areas after exposure R_(s) (Ω/square) of 4.8 × 10⁴1.6 × 10⁴ 1.5 × 10⁵ 1.2 × 10⁴  1.2 × 10⁴  1.0 × 10⁶ 1.1 × 10⁴  1.2 × 10⁶4.8 × 10⁵ 5.1 × 10⁴ exposed areas after exposure and processing R_(s)ratio non- 5 26.3 4.2   5 × 10⁸    5 × 10⁸  990   4 × 10⁸  7.5 2.0 2.2exposed/exposed areas

[0145] The results given in Table 6 indicate that the concentration ofNDP04 in the PEDOT/PSS-containing outermost layer had a considerableeffect on the resistance ratio non-exposed/exposed areas observed i.e.on the differentiation after processing between exposed and non-exposedareas, varying in the case of Support nr. 1 from 4 to 26.3.

[0146] The results given in Table 6 also indicate that the particularsupport used had a crucial effect on the resistance rationon-exposed/exposed areas, i.e. on the differentiation after processingbetween exposed and non-exposed areas, varying from 2 to 5×10⁸Particularly high resistance ratios of >10 were observed in the cases ofSupport nr. 2, 3 and 5 i.e. with supports treated with a coronadischarge or a glow discharge or a support in which the particularsubbing layer of Support nr. 5 was used. In the cases of samples XV, XVIand XVII coated on Support nr. 1, surface resistivities >10⁷ Ω/squarecould be obtained by rubbing thoroughly with a tissue during processing(results not shown in Table 6).

[0147] The mask used for exposing the above samples consisted ofalternating lines of high and low density, the lines having width downto 6 am. These lines were reproduced very well in the patternedmaterial, which showed conducting lines and non-conducting spaces ofsimilar width.

EXAMPLE 4

[0148] In EXAMPLE 4, various copolymers incorporating ADS-MONOMER 01were incorporated into the PEDOT/PSS-containing outermost layer torealize patterning of a polythiophene outermost layer. Samples XXV toXXX were produced by coating 50 mL m² of the dispersions given in Table7 on Support nr. 3, a polyethylene terephthalate film treated with aglow discharge to a wet thickness of 50 μm. TABLE 7 SAMPLE INGREDIENT[g] XXV XXVI XXVII XXVIII XXIX XXX 1.2% aq. PEDOT/PSS dispersion 16.716.7 16.7 16.7 16.7 16.7 2% aq. sol. of ZONYL ™ FSO 100 0.50 0.50 0.500.50 0.50 0.50 N-methyl-pyrrolidinone 2.50 2.50 2.50 2.50 2.50 2.50 2.5%aqueous NH₄OH solution 0.45 0.45 0.45 0.45 0.45 0.45 15.16% aq. solutionof NDP06 0.66 — — — — — 17.03% aq. solution of NDP07* — 0.59 — — — —18.34% aq. solution of NDP08* — — 0.54 — — — 16.8% ag. solution ofNDP09* — — — 0.59 — — 17.39% aq. solution of NDP10* — — — — 0.57 —16.63% aq. solution of NDP11* — — — — — 0.60 deionized water 29.19 29.2629.31 29.26 29.28 29.25 COVERAGE PEDOT/PSS [mg/m²] 200 200 200 200 200200 NDP06 [mg/m²] 100 — — — — — NDP07 [mg/m²] — 100 — — — — NDP08[mg/m²] — — 100 — — — NDP09 [mg/m²] — — — 100 — — NDP10 [mg/m²] — — — —100 — NDP11 [mg/m²] — — — — — 100 ZONYL FSO 100 [mg/m²] 8 8 8 8 8 8

[0149] The Samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 200s at 4 mW/cm²(=exposure of 0.8 J/cm²) and processed in water (softly rubbing with atissue under water). The results are given in Table 8.

[0150] The results in Table 8 show that Samples XXV to XXX exhibitedsurface resistivity ratios of non-exposed to exposed areas afterprocessing of greater than 2200. TABLE 8 SAMPLE PROPERTY XXV XXVI XXVIIXXVIII XXIX XXX R_(s)(Ω/square) of coated 3.2 × 10³ 4.5 × 10³ 3.4 × 10³3.8 × 10³ 3.2 × 10³ 2.9 × 10³ layer before patterning R_(s)(Ω/square) ofnon- >4.0 × 10⁷ >4.0 × 10⁷ >4.0 × 10⁷ >4.0 × 10⁷ >4.0 × 10⁷ >4.0 × 10⁷exposed areas after exposure and processing R_(s)(Ω/square) of 1.5 × 10⁴1.8 × 10⁴ 1.5 × 10⁴ 1.5 × 10⁴ 1.0 × 10⁴ 1.2 × 10⁴ exposed areas afterexposure and processing R_(s) rationon-exposed/ >2700 >2200 >2700 >2700 >4000 >3300 exposed areas

EXAMPLE 5

[0151] In EXAMPLE 5, Samples XXX1 to XXXIV were prepared by firstpreparing the dispersions given in Table 9 by adding a solution of acopolymer incorporating ADS-MONOMER 01 and N-methyl-pyrrolidinone to anaqueous PEDOT/PSS-dispersion. 50 mL/m² of these dispersions was thencoated onto Support nr. 3, a polyethylene terephthalate film treatedwith a glow discharge, to a wet thickness of 50, μm and dried to thecompositions given in Table 9. TABLE 9 composition of the coatingdispersions SAMPLE INGREDIENT XXXl XXXII XXXIII XXXIV 1.2% aq.dispersion of 16.7 16.7 16.7 16.7 PEDOT/PSS 2% aq. solution of 0.50 0.500.50 0.50 ZONYL ™ PSO 100 N-methyl-pyrrolidinone 2.50 2.50 2.50 2.502.5% aqueous NH₄OH solution 0.45 0.45 0.45 0.45 15.16% aq. solution ofNDP06 0.66 — — — 15.9% aq. solution of NDP12* — 0.63 — — 15.9% aq.solution of NDP13* — — 0.63 — 15.9% aq. solution of NDP14* — — — 0.63deionized water 29.19 29.22 29.22 29.22 COVERAGE PEDOT/PSS [mg/m²] 200200 200 200 NDP06 [mg/m²] 100 — — — NDP12 [mg/m²] — 100 — — NDP13[mg/m²] — — 100 — NDPl4 [mg/m²] — — — 100 ZONYL PSO 100 [mg/m²] 8 8 8 8

[0152] Since the conductivity-enhancing liquid N-methyl-pyrrolidinone ispresent in the coating dispersions conductivity enhancement takes placeduring the coating process resulting in PEDOT/PSS-outermost layers witha lower surface resistivity than such outermost layers prepared in theabsence of N-methyl-pyrrolidinone, as taught in EP-A 686 662 and EP-A 1003 179.

[0153] The Samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 200s at 4 mW/cm²(=exposure of 0.8 J/cm²) and processed in water (softly rubbing with atissue under water) and the results are given in Table 10.

[0154] The results in Table 10 show that Samples XXXI to XXXIV exhibitedsurface resistivity ratios of non-exposed to exposed areas afterprocessing of greater than 9000. TABLE 10 SAMPLE PROPERTY XXXI XXXIIXXXIII XXXIV R_(s)(Ω/square) of coated 2.8 × 10³ 1.9 × 10³ 1.6 × 10³ 1.8× 10³ layer before patterning R_(s)(Ω/square) of non- >4.0 × 10⁷ >4.0 ×10⁷ >4.0 × 10⁷ 1.6 × 10⁸ exposed areas after exposure and processingR_(s)(Ω/square) of exposed 1.0 × 10⁴ 3.6 × 10³ 4.5 × 10³ 4.2 × 10³ areasafter exposure and processing Resistance ratio non- >4 × 10³ >1.1 ×10³ >9 × 10³ 3.8 × 10⁴ exposed/exposed areas Optical resolution of 8 440 4 lines [μm] Optical resolution of >70 6 6 6 spaces μm]

EXAMPLE 6

[0155] In EXAMPLE 6, Samples XXXV to XL were prepared by first preparingthe dispersions given in Table 11 by adding a solution of a copolymerincorporating ADS-MONOMER 01 to an aqueous PEDOT/PSS-dispersion. 40mL/m² of these dispersions was then coated onto Support nr. 3, apolyethylene terephthalate film treated with a glow discharge to a wetthickness of 40 μm and dried. Since no conductivity-enhancing liquid ispresent in the coating dispersions, no conductivity enhancement takesplace during the coating process resulting in PEDOT/PSS-containingoutermost layers with a higher surface resistivity than would otherwisehave been the case. TABLE 11 composition of the coating dispersionsSAMPLE INGREDIENT [g] XXXV XXXVI XXXVII XXXVIII XXXIX XL 1.2% aq.PEDOT/PSS dispersion 16.7 16.7 16.7 16.7 16.7 16.7 2% aq. sol. ZONYL ™FSO 100 0.50 0.50 0.50 0.50 0.50 0.50 2.5% aqueous NH₄OH solution 0.500.50 0.50 0.50 0.50 0.50 15.9% solution of NDP15* 0.63 — — — — — 17.6%solution of NDP20* — 0.57 — — — — 17.4% solution of NDP21* — — 0.58 — —— 14.02% solution of NDP23* — — — 0.72 — — 14.36% solution of NDP27* — —— — 0.70 — 18.81% solution of NDP32* — — — — — 0.53 deionized water31.67 31.73 31.72 31.58 31.60 31.77 COVERAGE PEDOT/PSS [mg/m²] 200 200200 200 200 200 NDP15 [mg/m²] 100 — — — — — NDP20 [mg/m²] — 100 — — — —NDP21 [mg/m²] — — 100 — — — NDP23 [mg/m²] — — — 100 — — NDP27 [mg/m²] —— — — 100 — NDP32 [mg/m²] — — — — — 100 ZONYL FSO 100 [mg/m²] 8 8 8 8 88

[0156] The Samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 100s at 4 mW/cm²(=exposure of 0.4 J/cm²) and processed by dipping and moving gently inwater (processing liquid A) or a 2.5% by weight aqueous ammonia solutionat 25° C. water (processing liquid B), rinsing with deionized water anddried at 50° C. for 4 minutes. The results are given in Table 12.

[0157] The samples were then subjected to conductivity enhancement bytreatment for 1 minute in a 10% aqueous solution of diethylene glycol, aconductivity enhancing liquid, at 25° C. followed by drying at 110° C.for 20 minutes. The surface resistivity of the exposed and unexposedareas were then remeasured. The enhanced surface resistivity values aregiven in Table 12. TABLE 12 SAMPLE PROPERTY XXXV XXXVI XXXVII XXXVIIIXXXIX XL processing liquid B B B A A A R_(s)(Ω/square) of coated 7.5 ×10⁶ 3.4 × 10⁶ 1.9 × 10⁶ 4.5 × 10⁶ 6.5 × 10⁶ 8.0 × 10⁶ layer beforepatterning R_(s)(Ω/square) of non- >4.0 × 10⁷ >4.0 × 10⁷ 8.6 × 10⁶ >4.0× 10⁷ >4.0 × 10⁷ >4.0 × 10⁷ exposed areas after exposure and processingR_(s)(Ω/square) of exposed 4.5 × 10⁶ 2.1 × 10⁶ 8.2 × 10⁶ 5.7 × 10⁶ 2.7 ×10⁶ 4.0 × 10⁶ areas after exposure and processing R_(s) rationon-exposed/ >8.9 >19.0 1.0 >7.0 >14.8 >10 exposed areas Opticalresolution of 4 4 4 4 4 4 lines [μm] Optical resolution of 6 6 6 6 6 4spaces [μm] R_(s)(Ω/square) of non- 9.0 × 10⁸ 1.2 × 10⁹ 1.1 × 10⁷ 4.3 ×10¹² 5.4 × 10¹⁰ 4.5 × 10¹² exposed areas after processing andenhancement R_(s)(Ω/square) of exposed 9.1 × 10³ 9.5 × 10³ 2.7 × 10⁴ 3.8× 10⁴ 4.0 × 10³ 5.9 × 10³ areas after exposure, processing andenhancement R_(s) ratio non- 9.9 × 10⁴ 1.3 × 10⁵ 400 1.13 × 10⁸ 1.35 ×10⁷ 7.6 × 10⁸ exposed/exposed areas after enhancement

[0158] EXAMPLE 6 showed that similar resistance ratio ofnon-exposed/exposed areas can be achieved starting from non-conductivityenhanced PEDOT/PSS-containing outermost layers as from conductivityenhanced PEDOT/PSS-containing outermost layers (see EXAMPLE 5), providedthat the structured outermost layers are post-treated with aconductivity enhancing liquid followed by drying/tempering at anappropriate temperature. It should be, however, pointed out thatpost-treatment with a conductivity enhancing liquid will also is enhancethe conductivity of any PEDOT/PSS remaining in the non-exposed areasshould the removal be incomplete.

EXAMPLE 7

[0159] Samples VIII, IX, X, XI and XII of EXAMPLE 2 were image-wiseexposed in heat-mode with a NdYAG laser (1064 nm) having a spot size of22 μm, a pitch of 11 Am and a scan speed of 2 m/s. The image plane powerwas set at 100 mW. The exposed samples were processed in water (softlyrubbing with a tissue under water) For the samples IX, X, XI and XIIstructured PEDOT/PSS-containing outermost layers s were obtained havinga similar surface resistivity as in EXAMPLE 2. For sample VIII(comparative example) no structured conducting PEDOT/PSS-containingoutermost layer was obtained, since the PEDOT/PSS-containing outermostlayer was removed in the non-exposed as well as in the exposed areas.The surface resistivity of the non-exposed areas was above 10⁴ Ω/square.A surface resistivity in the non-exposed areas above 10¹⁰ Ω/square couldbe obtained when the material was rubbed thoroughly with a tissue duringprocessing.

EXAMPLE 8

[0160] Samples VIII, IX, X, XI and XII of EXAMPLE 2 were image-wiseexposed in heat-mode with a diode laser (830 nm) having a spot size of11 am, a pitch of 6 μm and a scan speed of 2 m/s. The image plane powerwas set at 81 mW. The exposed samples were processed in water (softlyrubbing with a tissue under water). The results were similar to thoseobtained in EXAMPLE 7.

EXAMPLE 9

[0161] EXAMPLE 9, a positive working light-sensitive compound was usedfor patterning a polythiophene outermost layer. Support nr. 1 was firstcoated with a solution of PQD0l in methylethylketone (1:2 volume:volume)(15 μm wet thickness). Samples XLI and XLII were prepared by coatingthis PQD01 layer with the PEDOT/SS-containing dispersions given in Table13 to a 67 μm wet thickness and drying. The PEDOT/PSS-containingoutermost layers of Samples XLI and XLII contained 100 and 400 ofPEDOT/PSS respectively. TABLE 13 composition of PEDOT/PSS-containingcoating dispersions SAMPLE INGREDIENT [g] XLI XLII 1.2% aqueousdispersion of PEDOT/PSS 125 500 Z6040 1.0 1.0 2% aqueous solution ofZONYL ™ FSO 100 1.5 1.5 N-methyl-pyrrolidinone 50 50 deionized water 825450 COVERAGE [mg/m²] PEDOT/PSS 100 400 ZONYL ™ FSO 100 2 8

[0162] Sample XLI was exposed from the PEDOT/PSS-containing layer sideof the support and Sample XLII from the uncoated side of the supporteach through a mask with a PRINTON CDL 1502i UV contact exposure unitfor 80s at 4 mW/cm² (=exposure of 0.32 J/cm²) and processed with AZ303(CLARIANT) for 80s. Image-wise structured conductingPEDOT/PSS-containing outermost layers were obtained. The patterningmethod of exposure and developing did not affect the conductivity of theoutermost layer. The surface resistivity of the non-exposed areas was1.6×10⁴ Ω/square in the case of Sample XLI and 1.2×10³ Ω/square in thecase of Sample XLII. A surface resistivity in the exposed areas above10¹⁰ Ω/square could be obtained when the material was rubbed thoroughlywith a tissue during processing. Resolutions of 20 μm and 50 μm wereobtained with Samples XLI and XLII respectively.

EXAMPLE 10

[0163] In EXAMPLE 10, a positive photo-sensitive compound and theelectroconductive polymer were present in the same layer. Support nr. 1was coated with 50 mL m² of the following coating dispersion (Table 14)(50 μm wet thickness). TABLE 14 composition of the coating dispersionsSAMPLE INGREDIENT XLIII 1.2% aqueous dispersion of PEDOT/PSS 300 PQD01100 1% aqueous solution of ZONYL ™ FSO 100 40 N-methyl-pyrrolidinone 560

[0164] The samples were exposed through a mask on a PRINTON CDL 1502i UVcontact exposure unit (from AGFA-GEVAERT N.V.) for 60s at 4 mW/cm²(=exposure of 0.24 J/cm²) and processed with AZ351B (CLARIANT).Image-wise structured conducting PEDOT/PSS-containing outermost layerswere obtained. The surface resistivity of the non-exposed areas afterdevelopment was 10⁴ Ω/square. A surface resistivity in the exposed areasabove 10¹⁰ Ω/square could be obtained when the material was rubbedthoroughly with a tissue or through a high pressure jet. A resolution of6 m was obtained.

EXAMPLE 11

[0165] In EXAMPLE 11, BADS01 and BADS02, negative workinglight-sensitive bis(aryldiazosulphonate) salts, were used for patterningthe light-exposure differentiable elements. Samples XLIV to L wereprepared by coating Support nr. 3 with 40 mL/m (40 μm wet thickness) ofthe coating dispersions given in Table 15, which did not contain aconductivity enhancing liquid. TABLE 15 SAMPLE INGREDIENT [g] XLIV XLVXLVI XLVII XLVIII XLIX L 1.2% aqueous dispersion 41.7 41.7 41.7 41.741.7 41.7 41.7 of PEDOT/PSS 2% aqueous solution of 1 1 1 1 1 1 1 ZONYL ™FSO 100 N-methyl-pyrrolidinone — — — — — — — BADS01 — 0.125 0.25 0.250.375 0.50 — BADS02 — — — — — — 0.25 deionized water 57.30 57.18 57.0557.05 56.93 56.80 57.05 COVERAGE PEDOT/PSS [mg/m²] 200 200 200 200 200200 200 BADS01 [mg/m²] — 50 100 100 150 200 100 % by weight of BADS01 025 50 50 75 100 — w.r.t. PEDOT/PSS ZONYL ™ FSO 100 [mg/m²] 8 8 8 8 8 8 8

[0166] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 400s at 4 mW/cm²(=exposure of 1.6 J/cm²) and rinsed with deionized water and dried at50° C. for 4 minutes. The surface resistivities of the non-exposed andexposed areas of the light-exposure differentiable element before andafter rinsing with water and drying are given in Table 16. TABLE 16SAMPLE XLIV XLV XLVI XLVII XLVIII XLIX L BADS01 [mg/m²] — 50 100 100 150200 — R_(s) of non-exposed layer 3.3 × 10⁶ 1.5 × 10⁶ 6.2 × 10⁴   4.5 ×10⁴   6.9 × 10³  1.1 × 10⁴  2.7 × 10⁶  untreated with water [Ω/square]R_(s) of non-exposed layer 4.7 × 10⁸ 1.1 × 10⁹   1 × 10¹²/ 5.0 × 10¹²/1.0 × 10¹³ 1.4 × 10¹⁴ 2.5 × 10¹⁴ rinsed with water 1.3 × 10¹⁴  7.3 ×10¹³  [Ω/square] R_(s) of exposed layer 3.0 × 10⁶ 1.1 × 10⁶ 1.7 × 10⁵  9.0 × 10⁴   2.6 × 10⁴  3.7 × 10⁴  1.0 × 10⁷  untreated with water[Ω/square] R_(s) of exposed layer 3.5 × 10⁸ 9.7 × 10⁵ 1.5 × 10⁵   9.9 ×10⁴   4.1 × 10⁴  4.1 × 10⁴  3.6 × 10⁸  rinsed with water [Ω/square]ratio of exposed layer 1.3 1134   7 × 10⁶/    5 × 10⁷/  2.4 × 10⁸  3.4 ×10⁹  6.9 × 10⁶  to unexposed layer   9 × 10⁸   7.3 × 10⁹   after rinsingwith water R_(s) of exposed layer — 1.4 × 10³ 1.6 × 10³   1.7 × 10³  3.3 × 10³  2.7 × 10³  1.0 × 10⁶  after rinsing with water [Ω/square] andconductivity enhancement

[0167] It was notable that a low surface resistivity was achieved withall the Samples containing BADS01, without the use of a conductivityenhancement treatment. No rubbing was necessary to lo remove theunexposed areas.

[0168] The results in Table 16 show that Samples XLIV to XLIX exhibiteddifferential surface resistivity between the exposed and unexposed areasof the surface of light-differentiable element containing BADS01 priorto conductivity enhancement with surface resistivity ratios of exposedto unexposed areas, which vary with BADS01 concentration. The highestsurface conductivity ratio prior to conductivity enhancement of 3.4×10⁹was observed for 100% by weight of BADS01 with respect to PEDOT/PSS (200mg/m² BADS01).

[0169] Conductivity enhancement reduced the surface resistivity of theexposed areas by up to a factor of 700, the amount of enhancementdecreasing with increasing BADS01 concentration indicating theconductivity enhancing properties of BADS01.

[0170] The differential surface conductivity realized with Sample L,whose light-differentiable element containing BADS02 was comparable withthat achieved with Samples XLV to XLIX, but the conductivity enhancementwith Sample L was markedly lower than for Samples XLV to XLIX.

EXAMPLE 12

[0171] EXAMPLE 12 differed from EXAMPLE 11 in that ammonia wasincorporated to improve the stability of the PEDOT/PSS-containingoutermost layer. Support nr. 3 was coated with 40 mL/m² (400 μm wetthickness) of the coating dispersions given in Table 17. TABLE 17 SAMPLELI (COMP) LII LIII INGREDIENT [g] 1.2% aq. PEDOT/PSS dispersion 41.741.7 41.7 2% aq. sol. of ZONYL ™ FSO 100 1 1 1 N-methyl-pyrrolidinone —— — BADS01 — 0.125 0.25 2.5% aqueous NH₄OH solution 2.28 2.48 2.33deionized water 55.02 54.70 54.72 COVERAGE PEDOT/PSS [mg/m²] 200 200 200BADS01 [mg/m²] — 50 100 ZONYL ™ FSO 100 [mg/m²] 8 8 8

[0172] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 250s at 4 mW/cm²(=exposure of 1.0 J/cm²) and rinsed with deionized water and dried at50° C. for 4 minutes. The surface resistivities of the non-exposed andexposed areas of the light-exposure differentiable element before andafter rinsing with water and drying are given in Table 18.

[0173] The results in Table 18 show that Samples LII and LIII exhibiteddifferential surface resistivity between the exposed and unexposed areasof the surface of light-differentiable element containing BADS01 priorto conductivity enhancement with surface resistivity ratios of exposedto unexposed areas, which vary with BADS01 concentration. The highestsurface conductivity ratio prior to conductivity enhancement of 4.4×10⁸was observed for 100 mg/m² BADS01.

[0174] Conductivity enhancement reduced the surface conductivity of theexposed areas by up to a factor of 700, the amount of enhancementdecreasing with increasing BADS01 concentration indicating theconductivity enhancing properties of BADS01. TABLE 18 SAMPLE LI (COMP)LII LIII R_(s) of non-exposed layer un- 3.2 × 10⁶ 1.4 × 10⁶ 6.3 × 10⁴rinsed with water [Ω/square] R_(s) of non-exposed layer rinsed  1.5 ×10¹⁰  7.1 × 10¹¹  2.0 × 10¹⁴ with water [Ω/square] R_(s) of exposedlayer unrinsed 3.0 × 10⁶ 4.8 × 10⁶ 4.5 × 10⁵ with water [Ω/square] R_(s)of exposed layer rinsed   7.9 × 10^(14*) 2.0 × 10⁶ 4.5 × 10⁵ with water[Ω/square] R_(s) ratio for exposed layer to — 3.6 × 10⁵ 4.4 × 10⁸unex-posed layer after rinsing with water Optical resolution [μm] none4-6 4-6 bubbles in surface of large — yes yes exposed areas surfaceresistivity of exposed — 1.4 × 10³ 2.1 × 10³ layer treated with water[Ω/square] and conductivity enhanced

EXAMPLE 13

[0175] In EXAMPLE 13, NDP33, a negative working light-sensitivecopolymer, was combined with BADS01 or BADS03, a negative workingbis(aryldiazosulphonate,) salt, and BADS03 alone were used forpatterning a polythiophene outermost layer. Samples LIV to LVII wereprepared by coating Support nr. 3 coated with 50 mL/m² (50 μm wetthickness) of the coating dispersions given in Table 19, which did notcontain a conductivity enhancing liquid. TABLE 19 composition of thecoating dispersions SAMPLE LIV LV LVI LVII INGREDIENT [g] 1.2% aq.dispersion of PEDOT/ 16.7 16.7 16.7 16.7 PSS 1% solution of BADS01 7.5 —— — 1% solution of BADS03 — 7.5 9.0 10.0 2.5% aqueous NH₄OH solution 1.11.0 0.8 1.0 15.9% solution of NDP33 in 0.16 0.16 0.38 —water/isopropanol 40/60 by volume 2% aq. solution of ZONYL ™ 0.5 0.5 0.50.5 FSO 100 N-methyl-pyrrolidinone — — — — deionized water 24.04 24.1422.63 21.8 pH 3.71 3.85 3.65 3.67 COVERAGE [mg/m²] PEDOT/PSS 200 200 200200 BADS01 75 — — — BADS03 — 75 90 100 NDP33 25 25 60 — ZONYL FSO 100 1010 10 10

[0176] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 150s at 4 mW/cm(=exposure of 0.6 J/cm²) and processed by dipping and moving gently in a2.5% by weight aqueous ammonia solution at 25° C. water, rinsing withdeionized water, drying at 50° C. for 4 minutes, treating with a 10%aqueous diethylene glycol solution for 1 minute thereby upgrading theconductivity and finally drying for 10 minutes at 110° C. The resultsare given in Table 20.

[0177] The results in Table 20 show that in the samples LIV to LVIIaccording to the invention structured conducting PEDOT/PSS-containingoutermost layers were obtained. The surface resistivity of thenon-exposed areas was below 10⁵ Ω/square and that of the non-exposedareas was >10¹³ Ω/square. The highest R, ratio non-exposed/exposed areasafter conductivity upgrading was observed for Sample LVI and LVII with acombination of BADS03 and NPD33; and only BADS03 respectively.

[0178] Unlike EXAMPLES 11 and 12 in which excellent R_(s) rationon-exposed/exposed areas were also observed after conductivityupgrading with BADS01 but bubbles were observed in the exposed areas,the use of a combination of the ADS-MONOMER 01-copolymer NDP33 andBADS01 produced no bubbles in the exposed areas. This is attributed tothe use of a combination of BADS01 and a ADS-MONOMER 01. TABLE 20 SAMPLEPROPERTY LIV LV LVI LVII Differentiation after processing YES YES YESYES between exposed and non-exposed areas R_(s) (Ω/square) of coatedlayer before 9.3 × 1.3 × 1.5 × 1.6 × patterning 10⁶ 10⁷ 10⁷ 10⁷ R_(s)(Ω/square) of large non-exposed 3.1 × 4.0 × 5.0 × 5.0 × areas afterconductivity upgrading 10¹³ 10¹³ 10¹⁴ 10¹⁴ R_(s) (Ω/square) of largeexposed areas 3.3 × 5.5 × 4.1 × 3.3 × after exposure, processing and 10³10³ 10³ 10³ conductivity upgrading R_(s) ratio non-exposed/exposed areas9.4 × 7.3 × 1.2 × 1.5 × after conductivity upgrading 10⁹ 10⁹ 10¹¹ 10¹¹optical resolution 4 μm 4 μm 4 μm 4 μm

EXAMPLE 14

[0179] In EXAMPLE 14, NDP15, a negative working light-sensitivecopolymer, was combined with BADS01, a negative workingbis(aryldiazosulphonate) compound, was used for patterning thelight-exposure differentiable element. Samples LVIII to LXII wereprepared by coating Support nr. 3 with 40 mL/m² (40 μm wet thickness) ofthe coating dispersions given in Table 21, which did not contain aconductivity enhancing liquid. TABLE 21 composition of the coatingdispersions SAMPLE LVIII LIX LX LXI LXII INGREDIENT [g] 1.2% aq.dispersion 41.7 41.7 41.7 41.7 41.7 of PEDOT/PSS 2% aq. solution of 1 11 1 1 ZONYL ™ FSO 100 BADS01 0.125 0.15 0.175 0.2 0.225 15.9% sol. ofNDP15 7.86 6.3 4.7 3.14 1.471 in water/isopropanol (40/60 by volume)N-methyl- — — — — — pyrrolidinone 2.5% aqueous NH₄OH 1.24 1.24 1.24 1.241.24 solution deionized water 48.08 49.16 51.19 52.72 54.36 pH 3.25 3.343.38 3.1 3.28 COVERAGE [mg/m²] PEDOT/PSS 200 200 200 200 200 BADS01 5060 70 80 90 NDP15 50 40 30 20 9 ZONYL FSO 100 8 8 8 8 8

[0180] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 400s at 4 mW/cm²(=exposure of 1.6 J/cm²) and processed by dipping and moving gently in a2.5% by weight aqueous ammonia solution at 25° C. water, rinsing withdeionized water, drying at 50° C. for 4 minutes, treating with a 10%aqueous diethylene glycol solution for 1 minute thereby upgrading theconductivity and finally drying for 10 minutes at 110° C. The resultsare given in Table 22. TABLE 22 SAMPLE PROPERTY LVIII LIX LX LXI LXIIDifferentiation after processing YES YES YES YES YES between exposed andnon-exposed areas R_(s) (Ω/square) of coated layer 1.3 × 1.1 × 4.1 × 4.1× 9.1 × before patterning 10⁷ 10⁷ 10⁶ 10⁶ 10⁵ R_(s) (Ω/square) of largenon-exposed 5.2 × 2.6 × 1.5 × 2.0 × 5.8 × areas after conductivityupgrading 10¹⁵ 10¹⁵ 10¹⁵ 10¹⁵ 10¹⁵ R_(s) (Ω/square) of exposed areas 1.8× 3.2 × 1.4 × 1.9 × 3.6 × after exposure, processing and 10³ 10³ 10³ 10³10³ conductivity upgrading R_(s) ratio non-exposed/exposed areas 2.9 ×8.1 × 1.1 × 1.1 × 1.6 × after conductivity upgrading 10¹² 10¹¹ 10¹² 10¹²10¹² bubbles in large areas? no no no yes yes

[0181] The results in Table 22 show that in the samples LVIII to LXIIaccording to the invention structured conducting PEDOT/PSS-containingoutermost layers were obtained. The surface resistivity of thenon-exposed areas was below 10⁴ Ω/square and that of the non-exposedareas was >10¹⁵ Ω/square. The highest R_(s) ratio non-exposed/exposedareas after conductivity upgrading, 2.9×10¹², was observed for SampleLVIII.

[0182] As with EXAMPLE 13 in which excellent R_(s) rationon-exposed/exposed areas were also observed after conductivityupgrading with a combination of an ADS-MONOMER 01-copolymer and BADS01,no bubbles were observed in large exposed areas for certain of theSamples: Samples LVIII, LIX and LX.

EXAMPLE 15

[0183] In EXAMPLE 15, NDP15, a negative working light-sensitivecopolymer, was combined with BADS01, a negative workingbis(aryldiazosulphonate) compound, was used for patterning thelight-exposure differentiable element. Samples LXIII to LXVII wereprepared by coating Support nr. 3 with 50 mL/m (50 μm wet thickness) ofthe coating dispersions given in Table 23, which did not contain aconductivity enhancing liquid. TABLE 23 composition of the coatingdispersions SAMPLE LXIII LXIV LXV LXVI LXVII INGREDIENT [g] 1.2% aq.dispersion of 16.7 16.7 16.7 16.7 16.7 PEDOT/PSS 2% aq. solution of 0.50.5 0.5 0.5 0.5 ZONYL ™ FSO 100 2.5% aqueous NH₄OH 0.5 0.5 0.5 0.5 0.5solution 1% aq. solution of — 2.5 5.0 7.5 10.0 BADS01 15.9% solution of0.63 0.47 0.32 0.16 — NDP15 water/isopro- panol 40/60 by volumeN-methyl-pyrrolidinone — — — — — deionized water 31.7 29.3 27.0 24.622.3 pH 3.3 3.3 3.3 3.3 3.3 COVERAGE [mg/m²] PEDOT/PSS 200 200 200 200200 BADS01 0 25 50 75 100 NDP15 100 75 50 25 0 ZONYL FSO 100 10 10 10 1010

[0184] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) at 4 mW/cm² for theexposure times given in Table 24 and processed by dipping and movinggently in a 2.5% by weight aqueous ammonia solution at 25° C. water,rinsing with deionized water, drying at 50° C. for 4 minutes, treatingwith a 10% aqueous diethylene glycol solution for 1 minute therebyupgrading the conductivity and finally drying for 10 minutes at 110° C.The results are given in Table 24. TABLE 24 SAMPLE PROPERTY LXIII LXIVLXV LXVI LXVII Exposure time [s] 100 100 100 100 300 Differentiationafter processing YES YES YES YES YES between exposed and non-exposedareas R_(s) (Ω/square) of coated layer 9.0 × 1.1 × 1.4 × 9.0 × 1.0 ×before patterning 10⁶ 10⁷ 10⁷ 10⁶ 10⁶ R_(s) (Ω/square) of largenon-exposed 1.7 × 1.5 × 1.2 × 5.5 × 3.5 × areas after processing and 10⁷10⁶ 10⁵ 10¹⁴ 10¹⁴ conductivity upgrading R_(s) (Ω/square) of exposedareas 1.4 × 8.2 × 5.5 × 7.4 × 7.8 × after exposure, processing and 10⁴10³ 10³ 10³ 10³ conductivity upgrading R_(s) ratio non-exposed/exposedareas 1.2 × 1.8 × 1.1 × 7.4 × 4.5 × after conductivity upgrading 10³ 10²10² 10¹⁰ 10¹⁰ Optical resolution of lines [μ]  4  4  4  4  4 Opticalresolution of spaces [μ]  4  4  4  4  4 bubbles in large areas? no no nono yes

[0185] The results in Table 24 show that in the samples LXIII to LXVIIaccording to the invention structured conducting PEDOT/PSS-containingoutermost layers were obtained. The surface resistivity of thenon-exposed areas was below 2×10⁴ Ω/square and that of the non-exposedareas varied considerably from 10⁵ to 10⁷ Ω/square for Samples LXIII toLXV to >10¹⁴ Ω/square for Samples LXVI and LXVII. The highest R_(s)ratio non-exposed/exposed areas after conductivity upgrading, 7.4×10¹⁰,was observed for Sample LXVI.

[0186] Only in the case of Sample LXVII were bubbles observed in largeexposed areas.

EXAMPLE 16

[0187] EXAMPLE 16, discloses the negative patterning performance ofdifferent layer configurations on Support nr. 1 and Support nr. 3. Thecompositions of the layers are given in Table 25. TABLE 25 SAMPLE LXVIIILXIX LXX LXXI LXXII LXXIII LXXIV Support nr. 1 1 1 1 3 3 3 LAYER 1 NDP04[mg/m²] 100 100 100 100 100 100 100 OUTERMOST LAYER 2 [mg/m²] PEDOT/PSS200 200 200 200 200 200 200 Z6040 200 70 — — 200 70 — NDP04 — — — 100 —— 100 N-methyl-pyrrolidinone 2500 2500 2500 — 2500 2500 2500

[0188] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) at 4 mW/cm² for thetimes given in Table 26 and processed by rinsing with deionized water.The surface resistivities of the non-exposed and exposed areas of thelight-exposure differentiable element before and after rinsing withdeionized water are given in Table 26. Only in the case of Sample LXXIwas rubbing with a soft tissue under water unnecessary. TABLE 26 SAMPLELXVIII LXIX LXX LXXI LXXII LXXIII LXXIV Support nr.  1  1  1  1  3  3  3Exposure times [s] 100 150 150 100 100 150 150 R_(s) of non-exposedareas 1.2 × 10⁴   4.2 × 10³  6.0 × 10³ 2.6 × 10⁷  1.5 × 10⁴   3.0 × 10³3.2 × 10⁵  unrinsed with water [Ω/square] R_(s) of non-exposed areas 6.2× 10¹² >4.0 × 10⁷ >4.0 × 10⁷ 3.2 × 10¹³ 4.6 × 10¹² >4.0 × 10⁷ 1.2 × 10¹³rinsed with water [Ω/square] R_(s) of exposed areas 1.1 × 10⁵   2.7 ×10⁴  3.0 × 10⁴ 1.13 × 10⁷   1.5 × 10⁵   2.1 × 10³ 1.0 × 10⁵  rinsed withwater [Ω/square] R_(s) ratio of exposed 5.6 × 10⁷  >1.5 × 10³ >1.3 × 10³2.8 × 10⁶  3.1 × 10⁷  >1.9 × 10⁴ 1.2 × 10⁸  areas to unexposed areasafter rinsing with water Resolution [μm] —  6 —  6  10 —  6

[0189] Despite Samples LXVIII, LXIX, LXX, LXXII and LXXIII only havingADS-MONOMER 01 homopolymer in the underlayer and thePEDOT/PSS-containing outermost layer being conductivity-enhanced as aresult of the presence of N-methyl-pyrrolidinone, moderate differentialsurface resistivities were observed with Samples LXIX, LXX and LXXIIIand considerable differential surface resistivities with Samples LXVIIIand LXXII. This shows that structuring of a PEDOT/PSS-containingoutermost layer is possible with UV-exposure of resins comprisingarylazosulphonate group in an adjacent layer. Samples LXXI and LXXIVwith the ADS-MONOMER 01 homopolymer in both the underlayer and thePEDOT/PSS-containing outermost layer adjacent thereto exhibitsconsiderable differential surface conductivities, whether or not thePEDOT/PSS-containing outermost layer is coated with the conductivityenhancing agent N-methyl-pyrrolidinone.

EXAMPLE 17

[0190] EXAMPLE 17, discloses the negative patterning performance ofdifferent layer configurations on Support nr. 1 and Support nr. 3. Thesupport used and the compositions of the layers are given in Table 27.Layers 1 and 2 were both coated to thicknesses of 50 μm. TABLE 27 SAMPLELXXV LXXVI LXXVII LXXVIII LXXIX LXXX Support nr. 1 1 1 3 3 3 LAYER 1 [g]15.9% sol. NDP14 in water/ 0.63 0.63 0.63 0.63 0.63 0.63 isopropanol(40/60 by vol.) 2% aq. sol. ZONYL FSO 100 0.5 0.5 0.5 0.5 0.5 0.5deionized water 48.87 48.87 48.87 48.87 48.87 48.87 OUTERMOST LAYER 2[g] 1.2% aq. PEDOT/PSS disp. 16.7 16.7 16.7 16.7 16.7 16.7 2% aq. sol.ZONYL FSO 100 0.5 0.5 0.5 0.5 0.5 0.5 2.5% aqueous NH₄OH 0.4 0.4 0.4 0.40.4 0.4 Z6040 0.07 — — 0.07 — — 15.9% sol. NDP14 in water/ — 0.63 0.63 —0.63 0.63 isopropanol (40/60 by vol.) N-methyl-pyrrolidinone 2.5 — 2.52.5 — 2.5 deionized water 29.83 31.77 29.27 29.83 31.77 29.27 pH 3.4 3.43.4 3.4 3.4 3.4 COVERAGE [mg/m²] LAYER 1 NDP14 100 100 100 100 100 100ZONYL FSO 100 10 10 10 10 10 10 OUTERMOST LAYER 2 [mg/m²] PEDOT/PSS 200200 200 200 200 200 3-glycidoxypropyl- 70 — — 70 — — trimethoxysilaneNDP14 — 100 100 — 100 100 ZONYL FSO 100 10 10 10 10 10 10

[0191] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit (from AGFA-GEVAERT N.V.) for 100s at 4 mW/cm²(=exposure of 0.4 J/cm²) and processed by rinsing with deionized water.No rubbing was for Samples LXXVI and LXXIX and soft rubbing was requiredfor Samples LXXVII and LXXX. The surface resistivities of thenon-exposed and exposed areas of the light-exposure differentiableelement before and after rinsing with deionized water are given in Table28.

[0192] Conductivity enhancement was then carried out on Samples LXXVIand LXXIX by dipping the developed materials in a 10% aqueousN-methyl-pyrrolidinone solution for 1 minute and then drying for 10minutes at 50° C. The surface resistivities of the non-exposed andexposed areas after conductivity enhancement are given in Table 28.TABLE 28 SAMPLE LXXV LXXVI LXXVII LXXVIII LXXIX LXXX Support nr. 1 1 1 33 3 R_(s) of non-exposed areas 4.5 × 1.7 × 5.3 × 4.9 × 1.3 × 4.0 ×unrinsed with water 10³ 10⁷ 10³ 10³ 10⁷ 10³ [Ω/square] R_(s) ofnon-exposed areas 3.7 × >4.0 × 6.3 × 1.2 × >4.0 × 1.55 × rinsed withwater 10⁵ 10⁷ 10⁶ 10¹³ 10⁷ 10¹³ [Ω/square] R_(s) of expoed areas 8.5 ×3.4 × 2.2 × 3.0 × 3.3 × 1.3 × rinsed with water 10³ 10⁶ 10⁴ 10⁴ 10⁶ 10⁴[Ω/square] R_(s) ratio of exposed 43.5 >11.8 2.9 4.0 × >12.1 1.2 × areasto unexposed 10⁸ 10⁹ areas after processing with water R_(s) (Ω/square)of large — 8.5 × — — 1.38 × — non-exposed areas after 10¹² 10¹³ totalprocessing including conductivity upgrading R_(s) (Ω/square) of — 2.9 ×— — 4.5 × — exposed areas after 10⁴ 10⁴ exposure, processing andconductivity upgrading R_(s) ratio of exposed — 2.9 × — — 3.1 × — areasto unexposed 10⁸ 10⁸ areas after processing and conductivity upgradingOptical resolution [μm] — 6 6 — 6 6

[0193] The results in Table 28 clearly show that for materials withoutermost layers coated from PEDOT/PSS-dispersions containingN-methyl-pyrrolidinone, a conductivity enhancing agent, Support nr. 3,glow discharge-treated polyethylene terephthalate film, gave a muchhigher R_(s) ratio of exposed areas to unexposed areas after processingthan materials coated on Support nr. 1. For Samples LXXVI and LXXIX withNDP14, a ADS-MONOMER 01 hydroxyethyl methacrylate copolymer, in both theunderlayer and the PEDOT/PSS-containing outermost layer and with thePEDOT/PS-containing outermost layers coated from PEDOT/PSS-dispersionsnot containing a conductivity-enhancing agent, this effect wasnegligible after conductivity enhancement with N-methyl-pyrrolidinone.

[0194] Materials coated on Support nr. 3 all showed very high R_(s)ratios of exposed areas to unexposed areas of at least 4×10⁸ formaterials with outermost layers coated from PEDOT/PSS-dispersionscontaining N-methyl-pyrrolidinone whether NDP14, a ADS-MONOMER 01hydroxyethyl methacrylate copolymer, was present in both the underlayerand the PEDOT/PSS-containing outermost layer or just in the underlayer.Furthermore Samples LXXVI and LXXIX with NDP14 in both the underlayerand the PEDOT/PSS-containing outermost layers and withPEDOT/PSS-containing outermost layers coated with PEDOT/PSS-dispersionsnot containing a conductivity-enhancing agent N-methyl-pyrrolidinoneexhibited very high R_(s) ratios of exposed areas to unexposed areas ofca. 3×10⁸ after conductivity upgrading with the conductivity enhancementagent N-methyl-pyrrolidinone.

[0195] This example showed that copolymers of an ADS-MONOMER were justas effective as light-sensitive components capable upon exposure ofchanging the removability of the exposed parts of thePEDOT/PSS-containing outermost layer relative to the unexposed parts ofthis outermost layer when incorporated in an adjacent layer to thePEDOT/PSS-containing outermost layer.

EXAMPLE 18

[0196] In EXAMPLE 18, different concentrations of BADS02, a negativeworking light-sensitive bis(aryldiazosulphonate) salt, were used in thePEDOT/PSS-containing outermost layer for patterning a polythiopheneoutermost layer. Support nr. 1 was coated with 40 mL/m² (40 μm wetthickness) of the coating dispersions given in Table 29. TABLE 29 SAMPLELXXXI INGREDIENT [g] (COMP) LXXXII LXXXIII LXXXIV LXXXV LXXXVI LXXXVIILXXXVIII 1.2% aq. PEDOT/PSS 41.7 41.7 41.7 41.7 41.7 41.7 41.7 41.7dispersion 2% aq. solution of 1 1 1 1 1 1 1 1 ZONYL ™ FSO 100 N-methyl-5 5 5 5 5 5 5 5 pyrrolidinone BADS02 0 0.025 0.0625 0.125 — 0.25 0.250.5 1% aq. sol. BADS02 — — — — 21.8 — — — deionized water 51.02 51.0050.96 50.90 21.5 50.99 51.15 51.12 2.5% aqueous NH₄OH 1.28 1.28 1.281.28 9.0 1.06 0.9 0.68 pH 3.41 3.3 3.17 3.45 3.26 3.53 2.6-2.8 3.55COVERAGE [mg/m²] PEDOT/PSS 200 200 200 200 200 200 200 200 BADS02 0 1025 50  87* 100 100 200 ZONYL ™ FSO 100 8 8 8 8  8 8 8 8

[0197] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit above the glass filter (from AGFA-GEVAERT N.V.)for 400s at 4 mW/cm² (=exposure of 1.6 J/cm²) and processed by rinsingwith deionized water. However, almost no difference was observed in thesurface resistivities whether exposure times of 100s or 400s were used,as long as subsequent rinsing with water was carried out. Thedegradation process appears to continue if the material is contactedwith water.

[0198] The surface resistivities of the non-exposed and exposed areas ofthe light-exposure differentiable element before and after rinsing withwater are given in Table 30. TABLE 30 SAMPLE LXXXI (COMP) LXXXII LXXXIIILXXXIV LXXXV LXXXVI LXXXVII LXXXVIII BADS02 [mg/m²] 0 10 25 50 87 100100 200 R_(s) of exposed 2.2 × 10³ 1.9 × 10⁴ 1.5 × 10⁵ 1.5 × 10⁶ 5.3 ×10⁶ 7.8 × 10⁶ 1.0 × 10⁷ 2.0 × 10⁷ layer unrinsed with water [Ω/square]R_(s) of exposed 2.9 × 10³ 3.4 × 10⁴ 4.9 × 10⁵ 7.2 × 10⁶ 6.7 × 10⁷ 1.1 ×10⁸ 1.5 × 10⁸ 1.1 × 10⁸ areas rinsed with water [Ω/square] R_(s) of non-2.1 × 10³ 2.5 × 10³ 3.3 × 10³ 5.9 × 10³ 6.2 × 10³ 1.2 × 10⁴ 1.3 × 10⁴6.5 × 10⁴ exposed areas un- rinsed with H₂O [Ω/square] R_(s) of non- 2.7× 10³ 3.8 × 10³ 5.1 × 10³ 1.1 × 10⁴ 6.2 × 10³ 2.1 × 10⁴ 1.8 × 10⁴ 1.4 ×10⁵ exposed areas rinsing with water [Ω/square] R_(s) ratio of 1.1 8.9596.1 654.5 10806 5238 8333 785.7 exposed areas to unexposed areas afterrinsing with water

[0199] The results in Table 30 show differential surface resistivitybetween the exposed and unexposed areas of the surface oflight-differentiable element containing BADS02 with surface resistivityratios of exposed to unexposed areas, which vary with BADS02concentration without removal of the non-exposed areas. The highestsurface conductivity ratio of 10⁴ was observed for 87 mg/m² BADS02(2.0×10⁻⁴ mol/m²).

[0200] When the light-exposure differentiable elements of Samples LXXXIIto LXXXVIII were then rubbed softly water-moistened tissues, thenon-exposed areas were removed thereby increasing the surfaceresistivity of the unexposed areas to ca. 10⁶ Ω/square. Stronger rubbingincreased the surface resistivity of the unexposed areas to 10¹⁰Ω/square.

EXAMPLE 19

[0201] In EXAMPLE 19, BADS01, BADS02 and BADS03, negative workinglight-sensitive bis(aryldiazosulphonate) salts, were used for patterninga polythiophene outermost layer. Samples LXXXIX to LCIII were preparedby coating Support nr. 1 with 40mL/m² (40 μm wet thickness) of thecoating dispersions given in Table 31 followed by drying at 50° C. for 5minutes except in the case of dispersions containing diethylene glycolwhich were dried at 110° C. for 5 minutes. TABLE 31 SAMPLE LXXXIX XC XCIXCII XCIII INGEDIENT [g] 1,2% aq. PEDOT/PSS 41.7 41.7 41.7 41.7 41.7dispersion 2% aq. sol. of ZONYL ™ FSO 1 1 1 1 1 100N-methyl-pyrrolidinone 5 — 5 — 5 diethylene glycol — — — 5 — BADS01 0.25— — — — BADS02 — 0.25 0.25 0.25 — 1% ag. solution of BADS03 — — — — 25deionized water 51.15 57.0 52.05 52.05 26.4 2.5% aqueous NH₄OH 0.9 — — —0.9 pH 2.6-2.8 — — — 2.31 COVERAGE PEDOT/PSS [mg/m²] 200 200 200 200 200BADS01 [mg/m²] 100 — — — — BADS02 [mg/m²] — 100 100 100 — BADS03 [mg/m²]— — — — 100 ZONYL ™ FSO 100 [mg/m²] 8 8 8 8 8

[0202] The samples were exposed through a mask on a PRINTON™ CDL 1502iUV contact exposure unit above the glass filter (from AGFA-GEVAERT N.V.)for 400s at 4 mW/cm² (=exposure of 1.6 J/cm²) and processed in a 2.5%aqueous NH₄OH solution and rinsed with deionized. The surfaceresistivities of the non-exposed and exposed areas of the light-exposuredifferentiable element before and after rinsing with water and drying at50° C. for 4 minutes are given in Table 32.

[0203] The results in Table 32 show differential surface resistivitybetween the exposed and unexposed areas of the surface oflight-differentiable element containing BAD01, BADS02 and BADS03 withsurface resistivity ratios of exposed to unexposed areas. The highestsurface conductivity ratio of 16,666 was observed for BADS02.

[0204] When the light-exposure differentiable elements of Samples LXXXIXto XCIII were then rubbed softly water-moistened tissues, thenon-exposed areas were removed thereby increasing the surfaceresistivity of the unexposed areas to ca. 10⁶ Ω/square. Stronger rubbingincreased the surface resistivity of the unexposed areas to 10¹⁰Ω/square. TABLE 32 SAMPLE LXXXIX XC XCI XCII XCIII R_(s) of exposedlayer 1.6 × 8.6 × 4.6 × 2.1 × 3.7 × untreated with water 10⁵ 10⁶ 10⁵ 10⁵10⁵ [Ω/square] R_(s) of exposed layer 6.1 × 2.5 × 2.0 × 4.6 × 2.6 ×rinsed with water 10⁵ 10^(14*) 10⁸ 10⁶ 10⁶ [Ω/square] R_(s) ofnon-exposed 1.2 × 9.2 × 5.3 × 2.9 × 1.4 × layer unrinsed with 10⁴ 10⁵10³ 10⁵ 10⁴ water [Ω/square] R_(s) of non-exposed 1.6 × 2.5 × 1.2 × 2.1× 2.3 × layer rinsed with water 10⁴ 10^(14*) 10⁴ 10⁶ 10⁴ [Ω/square]R_(s) ratio of exposed 38 1.0 16,666 2.2 113 layer to unexposed layerafter rinsing with water

[0205] The present invention may include any feature or combination offeatures disclosed herein either implicitly or explicitly or anygeneralisation thereof irrespective of whether it relates to thepresently claimed invention. In view of the foregoing description itwill be evident to a person skilled in the art that variousmodifications may be made within the scope of the invention.

What is claimed is:
 1. A material for making an electroconductivepattern, said material comprising a support and a light-exposuredifferentiable element, characterized in that said light-exposuredifferentiable element comprises an outermost layer containing apolyanion and a polymer or copolymer of a substituted or unsubstitutedthiophene, and optionally a second layer contiguous with said outermostlayer; and wherein said outermost layer and/or said optional secondlayer contains a light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of said outermost layerrelative to the unexposed parts of said outermost layer.
 2. Materialaccording to claim 1, wherein said polymer of a substituted orunsubstituted thiophene corresponds to formula (II):

in which n is larger than 1 and each of R¹ and R² independentlyrepresent hydrogen or an optionally substituted C₁₋₄ alkyl group ortogether represent an optionally substituted C₁₋₄ alkylene group or anoptionally substituted cycloalkylene group, preferably an ethylenegroup, an optionally alkyl-substituted methylene group, an optionallyC₁₋₁₂ alkyl- or phenyl-substituted ethylene group, a 1,3-propylene groupor a 1,2-cyclohexylene group.
 3. Material according to claim 1, whereinsaid polyanion is poly(styrene sulphonate).
 4. Material according toclaim 1, wherein said outermost layer has a surface resistivity lowerthan 10⁶ Ω/square.
 5. Material according to claim 1, wherein saidlight-sensitive component capable upon exposure of changing theremovability of the exposed parts of said outermost layer relative tothe unexposed parts of said outermost layer is a multidiazonium salt ora resin comprising a diazonium salt which reduces the removability ofexposed parts of said outermost layer.
 6. Material according to claim 1,wherein said light-sensitive component capable upon exposure of changingthe removability of the exposed parts of said outermost layer relativeto the unexposed parts of said outermost layer is abis(aryldiazosulphonate) salt, a tris(aryldiazosulphonate) salt or atetrakis(aryldiazosulphonate) salt which reduces the removability ofexposed parts of said outermost layer.
 7. Material according to claim 1,wherein said light-sensitive component capable upon exposure of changingthe removability of the exposed parts of said outermost layer relativeto the unexposed parts of said outermost layer is abis(aryldiazosulphonate) salt, which reduces the removability of exposedparts of said outermost layer, according to formula (I):MO₃S—N═N—Ar—L—Ar—N═N—SO₃M   (I) where Ar is a substituted orunsubstituted aryl group, L is a divalent linking group, and M is acation.
 8. Material according to claim 6, wherein saidbis(aryldiazosulphonate) salt is selected from the group consisting of


9. Material according to claim 1, wherein said light-sensitive componentcapable upon exposure of changing the removability of the exposed partsof said outermost layer relative to the unexposed parts of saidoutermost layer is a polymer or copolymer of an aryldiazosulphonatewhich reduces the removability of exposed parts of said outermost layer.10. Material according to claim 9, wherein in said light-exposuredifferentiable element the weight ratio of said polymer or copolymer ofan aryldiazosulphonate to said polymer or copolymer of a substituted orunsubstituted thiophene is between 10:200 and 400:200.
 11. Materialaccording to claim 1, wherein said light-sensitive component capableupon exposure of changing the removability of the exposed parts of saidoutermost layer relative to the unexposed parts of said outermost layeris a quinonediazide compound which increases the removability of exposedparts of said outermost layer.
 12. Material according to claim 1,wherein said support is treated with a corona discharge or a glowdischarge.
 13. Method of making an electroconductive pattern on asupport comprising the steps of: providing a material for making anelectroconductive pattern, said material comprising a support and alight-exposure differentiable element, wherein said light-exposuredifferentiable element comprises an outermost layer containing apolyanion and a polymer or copolymer of a substituted or unsubstitutedthiophene, and optionally a second layer contiguous with said outermostlayer; and wherein said outermost layer and/or said optional secondlayer contains a light-sensitive component capable upon exposure ofchanging the removability of the exposed parts of said outermost layerrelative to the unexposed parts of said outermost layer; image-wiseexposing said material thereby obtaining a differentiation of theremovability, optionally with a developer, of said exposed and saidnon-exposed areas of said outermost layer; processing said material,optionally with said developer, thereby removing areas of said outermostlayer; and optionally treating said material to increase theelectroconductivity of said non-removed areas of said outermost layer.14. Method according to claim 13, wherein said non-removed areas of saidoutermost layer have a surface resistivity lower than 10⁶ Ω/square. 15.Method according to claim 13, wherein said non-removed areas of saidoutermost layer have a surface resistivity lower than 10⁴ Ω/square. 16.Method of making an electroconductive pattern on a support without aremoval step comprising the steps of: providing a material for making anelectroconductive pattern, said material comprising a support and alight-exposure differentiable element, characterized in that saidlight-exposure differentiable element comprises an outermost layercontaining a polyanion and a polymer or copolymer of a substituted orunsubstituted thiophene having a surface resistivity lower than 10⁶Ω/square, and optionally a second layer contiguous with said outermostlayer; and wherein said outermost layer and/or said optional secondlayer contains an aryl diazosulfonate according to formula (I)MO₃S—N═N—Ar—L—Ar—N═N—SO₃M   (I) where Ar is a substituted orunsubstituted aryl group, L is a divalent linking group, and M is acation; capable upon exposure of changing the removability of theexposed parts of said outermost layer relative to the unexposed parts ofsaid outermost layer; and image-wise exposing the material therebyobtaining reduction in the conductivity of the exposed areas relative tonon-exposed areas, optionally with a developer.
 17. Method of making anelectroconductive pattern on a support without a removal step accordingto claim 16, wherein said bis(aryldiazosulfonate) compound according toformula (I) is selected from the group consisting of